Inorganic Reactions and Methods Volume 6
Inorganic Reactions and Methods Editor Arlan D. Norman Department of Chemistry University of Colorado Boulder, CO 80309-0215 Editorial Advisory Board Professor N. Bartlett Department of Chemistry University of California at Berkeley Berkeley, California 94720 Professor F.A. Cotton Department of Chemistry Texas A&M University College Station, Texas 77840 Professor E.O. Fischer Anorganisch-chemisches Laboratorium der Technischen Universitat 0-8046 Garching Lichtenbergestrasse 4 Germany Professor P. Hagenmuller Laboratoire de Chemie du Solide du C.N.R.S. 351 cours de la Liberation F-33405 Talence France Professor M.F. Lappert The Chemical Laboratory University of Sussex Falmer, Brighton, BN1 9QJ England
Professor A.G. MacDiarmid Department of Chemistry University of Pennsylvania Philadelphia, Pennsylvania 19174
Professor M. Schmidt lnstitut fur Anorganische Chemie der Universitat D-8700 Wurzburg Am Hubland Germany Professor H. Taube Department of Chemistry Stanford University Stanford, California 94305 Professor L.M. Venanzi Laboratorium fur Anorganische Chemie der ETH CH-80006 Zurich Universitatsstrasse 5 Switzerland
0 1998 Wiley-VCH, Inc.
Inorganic Reactions and Methods
Volume 6 Formation of Bonds to 0 , S, Se, Te, Po (Part 2)
Founding Editor
J. J. Zuckerman Editor
A. D. Norman
@3 W I LEY-VCH -
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New York Chichester Weinheim Brisbane Singapore * Toronto
This book is printed on acid-free paper.
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Copyright 0 1998 by Wiley-VCH, Inc. All rights reserved Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley i3 Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-601 1, fax (212) 850-6008, E-Mail:
[email protected]. Library of Congress Catalog Card Number: 85-15627 ISBN 0-471-24677-8
10 9 8 7 6 5 4 3 2 1
Contents of Volume 6 How to use this Book Preface to the Series Editorial Consultants to the Series Contributors to Volume 6
3.7
3.7.1 3.7.2 3.7.2.1 3.7.2.1.1 3.7.2.1.2 3.7.2.1.3 3.7.2.2 3.7.2.2.1 3.7.2.2.2 3.7.2.3 3.7.2.3.1 3.7.2.3.2 3.7.2.4
3.7.2.4.1 3.7.2.4.2 3.7.2.5
Formation of the Group VIB (0,S, Se, Te, Po)Group IB (Cu, Ag, Au) or IIB (Zn, Cd, Hg) Metal Bond Introduction Formation of the Oxygen-Group IB or IIB Bond From Dioxygen and Ozone By Reaction with the Metal By Addition to Low-Valent and Unsaturated Metal Complexes By Insertion into Metal-Ligand Bonds From Water and Alcohols By Reaction with Elements By Hydrolysis or Alcoholysis of Metal-Ligand Bonds From Hydrogen Peroxide and Organic Peroxides By Oxidation of the Metals and Their Complexes By Oxidation of the Ligands Coordinated to the Metals From Neutral Oxygen Donor Ligands [Ethers, Aldehydes, Ketones, Pyridine N-Oxides, Phosphine Oxides, Arsine Oxides and Dialkyl(ary1) Sulfoxides] By Ligand Displacement Reactions with Transition Metal Complexes By Insertion into the Metal-Ligand Bonds From Bidentate and Polydentate Oxygen Donor Ligands (from Polyethers and Crown Ethers, Macrocycles, 2,4-Pentanedione, etc.)
xvii xxiii xxvii xxix
1
4 6 6
7
7 7
a
9 V
vi
3.7.2.6 3.7.2.6.1 3.7.2.6.2 3.7.2.6.3 3.7.2.7 3.7.2.7.1 3.7.2.7.2 3.7.2.8 3.7.3 3.7.3.1 3.7.3.1.1 3.7.3.1.2 3.7.3.2 3.7.3.3 3.7.3.4 3.7.3.4.1 3.7.3.4.2 3.7.3.5 3.7.3.5.1 3.7.3.5.2 3.7.3.6 3.7.3.7 3.7.4 3.7.4.1 3.7.4.1.1 3.7.4.1.2 3.7.4.1.3
Contents of Volume 6
From Oxides of the Main Group Elements By Reaction with the Metals By Reaction with Complexes of the Metals By Insertion into Metal-Ligand Bonds From OH-, OR-, Og-, 0; By Ligand Substitution Reactions with Complexes of the Metals By Oxidation of the Metals and Their Complexes By Metal Atom and Related Reactions Formation of the Bond Between Sulfur and a Group IB or IIB Element From Sulfur By Direct Reaction with Metals By Reaction with Metal Complexes From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols From Thiocarbonyls, Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands From Organic Thio Acids and Other Thio Acids of Main Group Elements By Oxidation of the Metals or Their Complexes By Ligand Replacement Reactions with Complexes of the Metals and by Sulfur Atom Abstraction From Bidentate and Polydentate Sulfur Donor Atoms By Sulfur Addition, Oxidation and Sulfur Abstraction Reactions By Ligand Substitution Reactions From Sulfur Containing Anions (S2-, S-, [HS-1, [RSl-) By Metal Atom and Related Reactions Formation of the Bond Between Selenium, Tellurium, and Polonium and Group IB or IIB Elements By Reactions with the Group IB and IIB Metals Formation of the Bond with Selenium Formation of the Bond with Tellurium Electrolytic Reactions Between the Elements
10 10 11 11 11 11 12 12 14 14 14 15 15 18 19 19 20 21 21 22 22 28 28 28 28 30 32
Contents of Volume 6 3.7.4.2 3.7.4.2.1 3.7.4.2.2 3.7.4.3 3.7.4.4 3.7.4.5 3.7.4.6 3.7.4.6.1 3.7.4.6.1.1 3.7.4.6.1.2 3.7.4.6.2 3.7.4.6.2.1 3.7.4.6.2.2 3.7.4.6.2.3 3.7.4.6.2.4 3.7.4.6.2.5 3.7.4.6.2.6 3.7.4.6.2.7 3.7.4.6.2.8 3.7.4.6.2.9 3.7.4.7
3.8
3.8.1 3.8.2
By Reaction with Group IB or Group IIB Metal Compounds Binary Compounds Ternary Comounds By Reactions of Binary Acids of Selenium and Tellurium and Their Derivatives with Metal Compounds By Reaction of Oxides of Selenium and Tellurium with Metal Compounds By Reactions of the Anions and Oxyanions of the Elements with Metal Compounds From Donor Ligands Incorporating the Elements Selenium and Tellurium By Reaction with the Metals Chemically Driven Reactions Electrochemically Driven Reactions By Reactions with Metal Compounds Reaction with Alkali Metal Selenides, Polyselenides, Tellurides, and PolytelIurides Reaction with Organochalcogenides Reaction with Organoselenols and Tellurols Reaction with Trimethylsilyl Chalcogenides Reaction with Dialkylselenocarbamates Reaction with Triphenylphosphine Chalcogenides Reaction with Selenocyanate and Selenourea Reaction with Tetrahydroselenophene and Tetrahydrotellurophene and Derivatives Reaction with Miscellaneous Ligands By Reaction with Selenium or Tellurium Compounds in Metal-Organic Chemical Vapor Deposition (MOCVD) and Related Reactions
Formation of Bonds Between the Group VIB (0,S, Se, Te, Po) Elements and Transition and Inner Transition Metals Introduction Formation of the Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond
vi i
33 33 34 35 37 37 39 39 39 40 40 41 43 44 45 46 46 47 49 49
50
54 54 54
viii
3.8.2.1 3.8.2.1.1 3.8.2.1.2 3.8.2.1.3 3.8.2.2 3.8.2.2.1 3.8.2.2.2 3.8.2.3 3.8.2.3.1 3.8.2.3.2 3.8.2.3.3 3.8.2.4 3.8.2.4.1 3.8.2.4.2 3.8.2.4.3 3.8.2.5 3.8.2.5.1 3.8.2.5.2 3.8.2.5.3 3.8.2.6 3.8.2.6.1 3.8.2.6.2
Contents of Volume 6
From Dioxygen and Ozone By Reaction with the Transition or Inner Transition Metal By Addition to Low-Valentand Unsaturated Metal Complexes By Insertion into Metal-Ligand Bonds From Water By Substitution of Transition and Inner Transition Metal Ligand Bonds By Hydrolysis of Transition and Inner Transition Metal-Ligand Bonds From Hydrogen Peroxide By Oxidation of Transition and Inner Transition Metal Elements and Their Complexes By Oxidation of a Ligand Coordinated to a Transition and Inner Transition Metal Complex (Insertion Reaction) By Homolytic Transition and Inner Transition Metal-Ligand Substitution Reactions From Alcohols and Phenols By Substitution of Transition and Inner Transition Metal-Ligand Bonds By Alcoholysis of Transition and Inner Transition Metal-Ligand Bonds By Oxidation of Transition and Inner Transition Metal-Ligand Bonds From Organic Peroxides By Oxidation of Transition and Inner Transition Metal-Ligand Bonds By Substitution Reactions of Transition and Inner Transition Metal-Ligand Bonds By Reaction with a Ligand Coordinated to Transition and Inner Transition Metal Elements From Neutral Oxygen Donor Ligands (R2C0, R2S0, R3P0, R3As0,etc.) By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes By Insertion into Transition and Inner Transition Metal-Ligand Bonds: R’R2C0
54 54 55 58 63 63 64 65 65 66 66 66 66 67 69 70 70
70 70
70 70 72
Contents of Volume 6 3.8.2.6.3 3.8.2.7 3.8.2.7.1 3.8.2.7.2 3.8.2.8 3.8.2.8.1 3.8.2.8.2 3.8.2.8.3 3.8.2.9 3.8.2.9.1 3.8.2.9.2 3.8.2.10 3.8.2.10.1 3.8.2.11 3.8.2.11.1 3.8.2.11.2 3.8.2.1 1.3 3.8.3 3.8.3.1 3.8.3.1.1 3.8.3.1.2 3.8.3.2 3.8.3.2.1
By Oxidation of the Transition and Inner Transition Metal Complexes (Ligand Degradation, Oxygen Abstraction) From Bidentate and Polydentate Oxygen Donor Ligands (Crown Ethers, Macrocycles, 2,4-Pentanedione, etc.) By Substitution of Transition and Inner Transition Metal-Ligand Bonds By Oxidation of Transition and Inner Transition Metal Complexes From Main Group Element Oxides By Direct Addition to the Transition and Inner Transition Metals and Their Complexes By Insertion into Transition and Inner Transition Metal Bonds By Oxidation of Transition and Inner Transition Metals and Their Compounds From OH-, 02-,O F , and 0;By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes By Oxidation of the Transition and Inner Transition Metals and Their Complexes From Alkoxide and Carboxylate Anions By Substitution of Transition and Inner Transition Metal-Ligand Bonds From Metal Atom and Related Reactions Abstraction and Electron Transfer Processes Oxidative Addition/Complexation Reactions Simple Orbital Mixing: Dioxygen and Carbon Dioxide with Metal Atoms Formation of the Sulfur-Transition and InnerTransition Metal Bond From Sulfur By Reaction with the Transition and Inner Transition Metal By Reaction with Transition Metal and Inner Transition Metal Compounds From Hydrogen Sulfide, Polysulfides, and Thiols By Substitution Reactions with Transition Metal and Inner Transition Metal Compounds
ix 72 73 73 75 76 76 76 76 78 78 79 79 79 82 82 83 83 84 84
84 85 86 86
X
3.8.3.2.2 3.8.3.2.3 3.8.3.3 3.8.3.4 3.8.3.4.1 3.8.3.4.2 3.8.3.4.3 3.8.3.5 3.8.3.5.1 3.8.3.5.2 3.8.3.6 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.8.3.7 3.8.3.7.1 3.8.3.7.2 3.8.4
3.9 3.9.1 3.9.2 3.9.3 3.9.4
Contents of Volume 6
By Insertion of Sulfur into Transition and Inner Transition Metal-Ligand Bonds By Oxidation of the Transition Metal and Inner Transition Metal Complexes From Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands From Organic Thioacids, Thiophosphates, Xanthates, and Other 1 , l -Dithio Compounds By Oxidation of the Metals and Their Complexes By Ligand Replacement Reactions with Complexes of the Metals By Insertion of CS2 (or P4ST0)into MetalLigand Bonds From Bidentate (excluding 1,l-dithiols) and Polydentate Sulfur Donor Ligands By Sulfur Addition, Oxidation, and Sulfur Abstraction Reactions By Ligand Substitution Reactions - , HS -, Sz - , RS -)From Sulfur Anions (S2 Transition and Inner Transition Metal Bonds With Sulfur Anions (S2- , [HS-I) With Polysulfido Anions (S; - ) With Organosulfur Anions ([RSl-) From Metal Atom and Related Reactions Abstraction Processes Oxidative Addition/Complexation Reactions Formation of the Selenium-, Tellurium-, and Polonium-Transition and Inner Transition Metal Bond
89 90 90 91 91 92 96 97 97 97 98 98 105 109 115 115 116 116
Formation of the Bond Between Group VIB (0,S, Se, Te, Po) and Group 0 124 (Noble Gas) Elements Introduction By Reactions of Xenon Fluorides and Oxyfluorides with Oxides and Oxysalts By Reaction of Xenon Fluorides and Oxyfluorides with Oxyacids and Their Derivatives Bonds Between Oxygen and Krypton or Radon
124 124
127 129
Contents of Volume 6
3.10 3.10.1 3.10.1.1 3.10.1.1.1 3.10.1.1.2 3.10.1.1.3 3.10.1.2 3.10.1.2.1 3.10.1.2.2 3.10.1.2.3 3.10.1.3 3.10.1.3.1 3.10.1.3.2 3.10.1 -3.3 3.10.1.4 3.10.1.4.1 3.10.1.4.2 3.10.1.5 3.10.1 5.1 3.10.1.5.2 3.10.1.5.3 3.10.1 -5.4 3.10.1.5.5 3.10.2 3.10.2.1 3.10.2.2 3.10.2.2.1 3.10.2.2.2 3.10.2.2.3 3.10.2.3 3.10.2.3.1
Formation of Non-stoichiometric Oxides Introduction Basic Defect Equilibria: Thermodynamic and Structural Principles Inherent Point Defect and Electron Band Equilibria External Equilibrium with Oxygen Fugacity Relations Between Nonstoichiometry and Physical Properties Nonstoichiometry and Shear Planes Introduction Structural Properties Stability Extended Defects Crystallographic Shear Tunnel and Pentagonal Column Phases Chemical Twinning and Related Structures Coherent lntergrowth Homologous Series Formed by Ordered Extended Defects Disordered Extended Defects Classification of Nonstoichiometric Oxides Oxide Phases with Narrow Composition Ranges Grossly Nonstoichiometric Phases Homologous Series of Metal Oxides Coherently lntergrown Structures Oxides with Modulated Structures Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper Binary Oxides with Narrow Chemically Insignificant Composition Range Binary Oxides with a Wide Composition Range Transition Metal Lower Oxides, TiO, VO, MnO, FeO, COO, NiO, NbO, and CunO Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides (Ce, Pr, and Tb higher oxides) Oxygen-Excess Fluorite Structures, UOn+ Multiple Oxides with Point Defect and Defect Complex Equilibria Doped Oxide Phases
xi
130 130 130 130 132 133 134 134 135 137 141 141 143 146 149 149 150 151 152 153 154 155 155 157 157 158 158 160 165 166 166
xii
3.10.2.3.2 3.10.2.3.3 3.10.2.3.4 3.10.2.3.5
3.10.3 3.10.3.1 3.10.3.1.1 3.10.3.1.2 3.10.3.1.3 3.1 0.3.2 3.10.3.2.1 3.10.3.2.1.1 3.10.3.2.1.2 3.10.3.2.1.3 3.10.3.2.1.4 3.10.3.2.1.5 3.10.3.2.2 3.10.3.2.2.1 3.10.3.2.2.2 3.10.3.2.2.3 3.10.3.2.3 3. 0.3.2.4 3. 0.3.2.4.1 3. 0.3.2.4.2
Contents of Volume 6
Point Defect Nonstoichiometry in Spinels and Related Oxides Wide-Range Nonstoichiometry: PerovskiteDerived Structures Wide-Range Nonstoichiometry: OxygenDeficient Fluorite Structures Wide-Range Nonstoichiometry: Mixed Cation Oxides. Induced Valence Effects by Substantial Substitution of Cations Having Different Valency Operationally NonstoichiometricOxide Phases Binary Oxides: Crystallographic Shear Structures Rutile-Related Structures Re03-Related Structures: Molybdenum and Tungsten Oxides Niobium Oxides and Related Structures Nonstoichiometric Layer Structure Oxides Layered Oxides Based on the Perovskite Structure lntergrowth of Pervoskite with Rock Salt Layers - Ruddlesden/Popper Phases High Temperature Superconducting Cuprates lntergrowth of Perovskite with “Bi2O2” Layers - Aurivillius Phases Brownmillerite Family (AM03),; AM02 Titanates and Niobates, A,M,03, + 2 and Molybdates, Cs2Mon03,+ Derived from the Perovskite Structure Oxides Based on the Spinel Structure: Hexagonal Ferrites, P-Alumina Oxide Types, and LixM204(M = Ti, V, Mn) Hexagonal Ferrites The P-Alumina Family LixM204(M = Ti, V, Mn) Phases lntergrowths of the Cage Oxide A3Ma02, with a Tunnel Structure, A3M6Si4026 Oxides with IntercalationStructures: Layers Built Up of Edge-Sharing Octahedra Vanadium Bronzes H,Mo03: Hydrogen-Intercalated Compounds of Molybdenum Trioxide
167 170 172
173 175 175 175 177 178 182 183 183 184
191 192 193 195 195 196 197 197 199 199 202
Contents of Volume 6
3.10.3.2.4.3 3.10.3.2.4.4 3.10.3.2.4.5 3.1 0.3.2.4.6 3.1 0.3.3 3.10.3.3.1 3.10.3.3.2 3.10.3.3.3 3.10.3.3.4 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.2 3.10.3.3.5.3 3.1 0.3.3.5.4 3.10.3.3.5.5 3.10.3.4 3.10.3.4.1 3.10.3.4.2 3.10.3.4.3 3.10.3.5
3.1 1 3.11.1 3.1 1.2
Molybdenum Bronzes A,Mo,O, A,M02 Oxides Another Family of A,M02 Oxides (M=V,Cr, Mn, Co, Ni; A = Li, Na) Titanates and Titanoniobates (or Tantalates) with a Layer Structure: Ion Exchange Properties Tunnel Structure Oxides Tungsten, Molybdenum Bronzes, and Related Structures Titanium Bronzes and Related Oxides Hollandite, Psilomelane, Ramsdellite, and Related Oxides Vanadium Bronzes with a ThreeDimensional Structure Complex Oxides with Host-Lattice Built up from Octahedra and Tetrahedra Phosphate Tungsten Bronzes (PTB) Phosphate Niobium Bronzes (PNB) Phosphate Molybdenum Oxides Other Reduced Transition Metal Phosphates Siliconiobdates, Silicotantalates, and Corresponding Germanium Compounds Adaptive Structures Oxides with Vernier-Type Adaption Structures Double Oxides Based on Tantalum Pentoxide and Related Phases The Metal Uranates and Related Oxides Mixed Valence, Mixed Anion Phases, Including Oxides with Cations of Variable Valence (or Mixed Cations) Balanced by Substitution of Altervalent Anions
Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides
xiii
203 207 210 21 1 214 215 222 225 228 228 229 233 237 239 239 240 24 1 245 249
250
251
Introduction 25 1 Chemical Bonding and Variation of Physical Properties by Means of Chemical Parameters 252
xiv
3.11.2.1 3.11.2.2 3.11.3 3.1 1.3.1 3.1 1.3.2 3.11.4 3.11.4.1 3.1 1.4.2 3.1 1.5 3.11.5.1 3.11.5.2 3.1 1.6 3.1 1.6.1 3.11.6.1.1 3.1 1.6.1.2 3.1 1.6.1.3 3.11.6.1.4 3.1 1.6.1.5 3.1 1.6.1.6 3.1 1.6.1.7 3.1 1.6.2 3.11.6.2.1 3.11.6.2.2 3.11.6.2.3 3.11.6.2.4 3.11.6.2.5 3.1 1.6.3 3.11.6.3.1 3.1 1.6.3.2 3.1 1.6.3.3 3.1 1.6.4 3.1 1.6.4.1 3.1 1.6.4.2
Contents of Volume 6
d-Transition Metal Chalconides 4f-Transition Metal (Rare Earth) Chalcogenides Synthesis and Crystal Growth Under Controlled Thermodynamic Parameters Control of Nonstoichiometry Chemical Vapor Transport of the Chalcogenides By Reactions in Chalcogen-Hydrogen Systems Of Metals Of Compounds of Metal By Precipitation Under Normal and Supercritical Conditions From Aqueous Solution From Non aqueous Solution By Insertion Reactions from Solution Layered Transition Metal Dichalcogenides Unsolvated Metal Intercalation Compounds: Alkali Metals Unsolvated Metal Intercalation Compounds: Posttransition Metals Unsolvated Metal Intercalation Compounds: Transition Metals “Misfit Layer Compounds” Solvated Phases Molecular Intercalation Compounds Complex Intercalated Species Other Layered Chalcogenides Ta2S2C,Nb2S2C K2Pf4S6 and A2M& MPX3 Li2FeS2,LiCuFeS2, NaCuFeS2and KCuFeS2 KCU& Chain Structures The Pseudo-One-Dimensional Compounds MX3 KFeS2 Az[M06X6] and [ M O ~ X ~ I ~ Framework Structures Structures with One-Dimensional Channels Structures with a Three-Dimensional Net of Channels
252 253 255 256 259 260 261 26 1 262 262 263 264 269 269 274 276 277 278 282 284 286 286 287 287 288 289 290 290 290 291 292 292 293
Contents of Volume 6
3.1 1.7 3.11.7.1 3.11.7.2
By Reactions in Melts In Molten Metals In Molten Salts
xv
295 296 296
Abbreviations
299
Author Index
307
Compound Index
349
Subject Index
489
How to Use this Book 1. Organization of Subject Matter 1.1. Logic of Subdivision and Add-on Chapters This volume is part of a series that describes all of inorganic reaction chemistry. The contents are subdivided systematically and so are the contents of the entire series. Using the periodic system as a correlative device, it is shown how bonds between pairs of elements can be made. Treatment begins with hydrogen making a bond to itself in H2 and proceeds according to the periodic table with the bonds formed by hydrogen to the halogens, the groups headed by oxygen, nitrogen, carbon, boron, beryllium and lithium, to the transition and inner-transition metals and to the members of group zero. Next it is considered how the halogens form bonds among themselves and then to the elements of the main groups VI to I, the transition and inner-transition metals and the zerogroup gases. The process repeats itself with descriptions of the members of each successive periodic group making bonds to all the remaining elements not yet treated until group zero is reached. At this point all actual as well as possible combinations have been covered. The focus is on the primary formation of bonds, not on subsequent reactions of the products to form other bonds. These latter reactions are covered at the places where the formation of those bonds is described. Reactions in which atoms merely change their oxidation states are not included, nor are reactions in which the same pairs of elements come together again in the product (for example, in metatheses or redistributions). Physical and spectroscopic properties or structural details of the products are not covered by the reaction volumes; the latter are concerned with synthetic utility based on yield, economy of ingredients, purity of product, specificity, etc. The preparation of short-lived transient species is not described. While in principle the systematization described above could suffice to deal with all the relevant material, there are other topics that inorganic chemists customarily identify as being useful in organizing reaction information and that do not fit into the scheme. These topics are the subject of eight additional chapters constituting the last four volumes of the series. These chapters are systematic only within their own confines. Their inclusion is based on the best judgment of the Editorial Advisory Board as to what would be most useful currently as well as effective in guiding the future of inorganic reaction chemistry. xvi i
xviii
How to Use this Book
1.2. Use of Decimal Section Numbers The organization of the material is readily apparent through the use of numbers of headings. Chapters are broken down into divisions, sections, and subsections, which have short descriptive headings and are numbered according to the following scheme: 1. Major Heading 1.1. Chapter Heading 1.1.1. Division Heading 1.1.1.1. Section Heading 1.1.1.1.1. Subsection Heading Further subdivision of a five-digit “slice” utilizes lower-case Roman numerals in parentheses: (i), (ii), (iii),etc. It is often found that as a consequence of the organization, cognate material is located in different chapters but in similarly numbered pieces, i.e., in parallel sections. Section numbers, rather than page numbers, are the key by which the material is accessed through the various indexes.
1.3. Building of Headings 1.3.1. Headings Forming Part of a Sentence
Most headings are sentence-fragment phrases which constitute sentences when combined. Usually a period signifies the end of a combined sentence. In order to reconstitute the context in which a heading is to be read superior-rank titles are printed as running heads on each age. When the sentences are put together from their constituent parts, they describe the contents of the piece at hand. For an example, see 2.3 below. 1.3.2. Headings Forming Part of an Enumeration
For some material it is not useful to construct title sentences as described above. In these cases hierarchical lists, in which the topics are enumerated, are more appropriate. To inform the reader fully about the nature of the material being described, the headings of connected sections that are superior in hierarchy always occur as running heads at the top of each page.
2. Access and Reference Tools 2.1. Plan of the Entire Series (Front Endpaper) Printed on the inside of the front cover is a list, compiled from all 18 reaction volumes, of the major and chapter headings, that is, all headings that
How to Use this Book
xix
are preceded by a one- or two-digit decimal section number. This list shows in which volumes the headings occur and highlights the contents of the volume that is at hand by means of a gray tint.
2.2. Contents of the Volume at Hand All the headings, down to the title of the smallest decimal-numbered subsection, are listed in the detailed table of contents of each volume. For each heading the table of contents shows the decimal section number by which it is preceded and the number of the page on which it is found. Beside the decimal section numbers, successive indentations reveal the hierarchy of the sections and thereby facilitate the comprehension of the phrase (or of the enumerative sequence) to which the headings of hierarchically successive sections combine. To reconstitute the context in which the heading of a section must be read to become meaningful, relevant headings of sections superior in hierarchy are repeated at the top of every page of the table of contents. The repetitive occurrences of these headings is indicated by the fact that position and page numbers are omitted.
2.3. Running Heads In order to indicate the hierarchical position of a section, the top of every page of text shows the headings of up to three connected sections that are superior in hierarchy. These running heads provide the context within which the title of the section under discussion becomes meaningful. As an example, the page of Volume 1 on which section 1.4.9.1.3 “in the Production of Methanol” starts, carries the running heads: 1.4. The Formation of Bonds between Hydrogen and 0, S, Se, Te, Po 1.4.9. by Industrial Processes 1.4.9.1. Involving Oxygen Compounds
whereby the phrase “in the Production of Methanol” is put into its proper perspective.
2.4. List of Abbreviations Preceding the indexes there is a list of those abbreviations that are frequently used in the text of the volume at hand or in companion volumes. This list varies somewhat in length from volume to volume; that is, it becomes more comprehensive as new volumes are published. Abbreviations that are used incidentally or have no general applicability are not included in the list but are explained at the place of occurrence in the text.
xx
How to Use this Book
2.5. Author Index The author index is compiled by computer from the lists of references. Thus it tells whose publications are cited and in that respect is comprehensive. It is not a list of authors, beyond those cited in the references, whose results are reported in the text. However, as the references cited are leading ones, consulting them, along with the use of appropriate works of the secondary literature, will rapidly lead to the complete literature related to any particular subject covered. Each entry in the author index refers the user to the appropriate section number.
2.6. Compound Index The compound index lists individual, fully specified compositions of matter that are mentioned in the text. It is an index of empirical formulas, ordered according to the following system: the elements within a given formula occur in alphabetical sequence except for C, or C and H if present, which always come first. Thus, the empirical formula for Ti(SO& is BH3.NH3 Be2C03 CsHBr, Al(HC03)3
08S2Ti BH6N CBe203 BrzCsH C3H3A109
The formulas themselves are ordered alphanumerically without exception; that is, the formulas listed above follow each other in the sequence BH6N, Br2CsH, CBe,O,, C3H3A109,08S2Ti. A compound index constructed by these principles tells whether a given compound is present. It cannot provide information about compound classes, for example, all aluminum derivatives or all compounds containing phosphorus. In order to open this route of access, as well, the compound index is augmented by successively permuted versions of all empirical formulas. Thus the number of appearances that an empirical formula makes in the compound index is equal to the number of elements it contains. As an example, C3H3A109, mentioned above, will appear as such and, at the appropriate positions in the alphanumeric sequence, as H3A10;C3, A10;C3H3 and O;C3H3Al. The asterisk identifies a permuted formula and allows the original formula to be reconstructed by shifting to the front the elements that follow the asterisk. Each nonpermuted formula is followed by linearized structural formulas that indicate how the elements are combined in groups. They reveal the connectivity of the compounds underlying each empirical formula and serve to distinguish substances which are identical in composition but differ in the arrangement of elements (isomers). As an example, the empirical formula C 4 H I 0 0
How to Use this Book
xxi
might be followed by the linearized structural formulas (CH3CH2)20, CH3(CH2)20CH3, (CH3)2CHOCH3,CH3(CH2)30H,(CH3)2CHCH20Hand CH3CH2(CH3)CHOHto identify the various ethers and alcohols that have the elemental composition C4HI00. Each linearized structural formula is followed in a third column by keywords describing the context in which it is discussed and by the number(s) of the section(s) in which it occurs.
2.7. Subject index The subject index provides access to the text by way of methods, techniques, reaction types, apparatus, effects and other phenomena. Also, it lists compound classes such as organotin compounds or rare-earth hydrides which cannot be expressed by the empirical formulas of the compound index. For multiple entries, additional keywords indicate contexts and thereby avoid the retrieval of information that is irrelevant to the user’s need. Again, section numbers are used to direct the reader to those positions in the book where substantial information is to be found.
2.8. Periodic Table (Back Endpaper) Reference to periodic groups avoids cumbersome enumerations. Section headings in the series employ the nomenclature. Unfortunately, however, there is at the present time no general agreement on group designations. In fact, the scheme that is most widely used (combining a group number with the letters A and B) is accompanied by two mutually contradictory interpretations. Thus, titanium may be a group IVA or group IVB element depending on the school to which one adheres or the part of the world in which one resides. In order to clarify the situation for the purposes of the series, a suitable labeled periodic table is printed on the inside back cover of each volume. All references to periodic group designations in the series refer to this scheme.
Preface to the Series Inorganic Reactions and Methods constitutes a closed-end series of books designed to present the state of the art of synthetic inorganic chemistry in an unprecedented manner. So far, access to knowledge in inorganic chemistry has been provided almost exclusively using the elements or classes of compounds as starting points. In the first 18 volumes of Inorganic Reactions and Methods, it is bond formation and type of reaction that form the basis of classification. This new route of access has required new approaches. Rather than sewing together a collection of review articles, a framework has had to be designed that reflects the creative potential of the science and is hoped to stimulate its further development by identifying areas of research that are most likely to be fruitful. The reaction volumes describe methods by which bonds between the elements can be formed. The work opens with hydrogen making a bond to itself in H2 and proceeds through the formation of bonds between hydrogen and the halogens, the groups headed by oxygen, nitrogen, carbon, boron, beryllium and lithium to the formation of bonds between hydrogen and the transition and inner-transition metals and elements of group zero. This pattern is repeated across the periodic system until all possible combinations of the elements have been treated. This plan allows most reaction topics to be included in the sequence where appropriate. Reaction types that do not arise from the systematics of the plan are brought together in the concluding chapters on oxidative addition and reductive elimination, insertions and their reverse, electron transfer and electrochemistry, photochemical and other energized reactions, oligomerization and polymerization, inorganic and bioinorganic catalysis and the formation of intercalation compounds and ceramics. The project has engaged a large number of the most able inorganic chemists as Editorial Advisors creating overall policy, as Editorial Consultants designing detailed plans for the subsections of the work, and as authors whose expertise has been crucial for the quality of the treatment. The conception of the series and the details of its technical realization were the subject of careful planning for several years. The distinguished chemists who form the Editorial Advisory Board have devoted themselves to this exercise, reflecting the great importance of the project. It was a consequence of the systematics of the overall plan that publication of a volume had to await delivery of its very last contribution. Thus was the defect side of the genius of the system revealed as the excruciating process of extracting the rate-limiting manuscripts began. Intense editorial effort was required in order to bring forth the work in a timely way. The production process had to be designed so that the insertion of new material was possible up to the very last stage, enabling authors to update their pieces with the latest xxiii
xxiv
Preface to the Series
developments. The publisher supported the cost of a computerized bibliographic search of the literature and a second one for updating. Each contribution has been subjected to an intensive process of scientific and linguistic editing in order to homogenize the numerous individual pieces, as well as to provide the highest practicable density of information. This had several important consequences. First, virtually all semblances of the authors’ individual styles have been excised. Second, it was learned during the editorial process that greater economy of language could be achieved by dropping conventionally employed modifiers (such as very) and eliminating italics used for emphasis, quotation marks around nonquoted words, or parentheses around phrases, the result being a gain in clarity and readability. Because the series focuses on the chemistry rather than the chemical literature, the need to tell who has reported what, how and when can be considered of secondary importance. This has made it possible to bring all sentences describing experiments into the present tense. Information on who published what is still to be found in the reference lists. A further consequence is that authors have been burdened neither with identifying leading practitioners, nor with attributing priority for discovery, a job that taxes even the talents of professional historians of science. The authors’ task then devolved to one of describing inorganic chemical reactions, with emphasis on synthetic utility, yield, economy, availability of starting materials, purity of product, specificity, side reactions, etc. The elimination of the names of people from the text is by far the most controversial feature. Chemistry is plagued by the use of nondescriptive names in place of more expository terms. We have everything from Abegg’s rule, Adkin’s catalyst, Admiralty brass, Alfven number, the Amadori rearrangement and Adurssov oxidation to the Zdanovskii law, Zeeman effect, Zincke cleavage and Zinin reduction. Even well-practiced chemists cannot define these terms percisely except for their own areas of specialty, and no single source exists to serve as a guide. Despite these arguments, the attempt to replace names of people by more descriptive phrases was met in many cases by a warmly negative reaction by our colleague authors, notwithstanding the obvious improvements wrought in terms of lucidity, freedom from obscurity and obfuscation and, especially, ease of access to information by the outsider or student. Further steps toward universality are taken by the replacement of element and compound names wherever possible by symbols and formulas, and by adding to data in older units their recalculated SI equivalents. The usefulness of the reference sections has been increased by giving journal-title abbreviations according to the Chemical Abstracts Service Source Index, by listing in each reference all of its authors and by accompanying references to patents and journals that may be difficult to access by their Chemical Abstracts citations. Mathematical signs and common abbreviations are employed to help condense prose and a glossary of the latter is provided in each volume. Dangerous or potentially dangerous procedures are high-lighted in safety notes printed in boldface type.
Preface to the Series
xxv
The organization of the material should become readily apparent from an examination of the headings listed in the table of contents. Combining the words constituting the headings, starting with the major heading (one digit) and continuing through the major chapter heading (two digits), division heading (three digits), section heading (four digits) to the subsection heading (five digits), reveals at once the subject of a “slice” of the plan. Each slice is a self-contained unit. It includes its own list of references and provides definitions of unusual terms that may be used in it. The reader, therefore, through the table of contents alone, can in most instances quickly reach the desired material and derive the information wanted. In addition there is for each volume an author index (derived from the lists of references) and a subject index that lists compound classes, methods, techniques, apparatus, effects and other phenomena. An index of empirical formulas is also provided. Here in each formula the element symbols are arranged in alphabetical order except that C, or C and H if present, always come first. Moreover, each empirical formula is permuted successively. Each permuted formula is placed in its alphabetical position and cross referenced to the original formula. Therefore, the number of appearances that an empirical formula makes in the index equals the number of its elements. By this procedure all compounds containing a given element come together in one place in the index. Each original empirical formula is followed by a linearized structural formula and keywords describing the context in which the compound is discussed. All indexes refer the user to subsection rather than page number. Because the choice of designations of groups in the periodic table is currently in a state of flux, it was decided to conform to the practice of several leading inorganic texts. To avoid confusion an appropriately labeled periodic table is printed on the back endpaper. From the nature of the work it is obvious that probably not more than two persons will ever read it entire: myself and the publisher’s copy editor, Arline Keithe, She, as well as Steven Bedney, Production Manager of VCH Publishers, are to be thanked for their unflagging devotion to the highest editorial standards. The original conception for this series was the brainchild of Dr. Hans F. Ebel, Director of the Editorial Department of VCH Verlagsgesellschaft in Weinheim, Federal Republic of Germany, who also played midwife at the birth of the plan of these reaction volumes with my former mentor, Professor Alan G. MacDiarmid of the University of Pennsylvania, and me in attendance, during the Anaheim, California, American Chemical Society Meeting in the Spring of 1978. Much of what has finally emerged is the product of the inventiveness and imagination of Professor Helmut Griinewald, President of VCH Verlagsgesellschaft. It is a pleasure to acknowledge that I have learned much from him during the course of our association. Ms. Nancy L. Burnett is to be thanked for typing everything that had to do with the series from its inception to this time. Directing an operation of this magnitude without her help would have been unimaginable. My wife Rose stood by with good cheer while two rooms of our
xxvi
Preface to the Series
home filled up with 10,000 manuscript pages, their copies and attendant correspondence. Finally, and most important, an enormous debt of gratitude toward all our authors is to be recorded. These experts were asked to prepare brief summaries of their knowledge, ordered in logical sequence by our plan. In addition, they often involved themselves in improving the original conception by recommending further refinements and elaborations. The plan of the work as it is being published can truly be said to be the product of the labors of the advisors and consultants on the editorial side as well as the many, many authors who were able to augment more general knowledge with their own detailed information and ideas. Because of the unusually strict requirements of the series, authors had not only to compose their pieces to fit within narrowly constrained limits of space, format and scope, but after delivery to a short deadline were expected to stand by while an intrusive editorial process homogenized their own prose styles out of existence and shrank the length of their expositions. These long-suffering colleagues had then to endure the wait for the very last manuscript scheduled for their volume to be delivered so that their work could be published, often after a further diligent search of the literature to insure that the latest discoveries were being cited and that claims for facts now proved false were eliminated. To these co-workers (270 for the reaction volumes alone), from whom so much was demanded but who continued to place their knowledge and talents unstintingly at the disposal of the project, we dedicate this series. J. J. ZUCKERMAN Norman, Oklahoma July 4, 1985 The JJZ vision of the Inorganic Reactions and Methods series, and the unique systemization of inorganic chemistry it embodies, continue as the series moves to completion. During the period of A. P. Hagen’s editorship and since, under my direction, every effort has been made to keep the style consistent with what was originally conceived. The continued development of this exciting series has depended upon the untiring efforts and patience of the many series authors and Barbara Goldman and Shirley Thomas of Wiley-VCH. I sincerely thank all these people for their patience and untiring efforts on behalf of this volume. A. D. NORMAN Boulder, Colorado July 10, 1993
Editorial Consultants to the Series Professor H. R. Allcock Pennsylvania State University
Professor W. L. Jolly University of California at Berkeley
Professor J. S. Anderson University of Aberystwyth
Professor C. B. Meyer University of Washington
Professor F. C. Anson California Institute of Technology
Professor H. Noth Universitat Miinchen
Dr. M. G. Barker University of Nottingham
Professor H. Nowotny University of Connecticut
Professor D. J. Cardin Trinity College Professor M. H. Chisholm Indiana University Professor C. Cros Laboratoire de Chemie du Solide du C.N.R.S. Dr. B. Darriet Laboratoire de Chemie du Solide du C.N.R.S. Professor E. A. V. Ebsworth University of Edinburgh Professor J. J. Eisch State University of New York at Binghamton
Dr. G. W. Parshall E.I. du Pont de Nemours Professor M. Pouchard Laboratoire de Chemie du Solide du C.N.R.S. Professor J. Rouxel Laboratoire de Chemie Minerale au C.N.R.S. Professor R. Schmutzler Technische Universitat Barunschweig Professor A. W. Searcy University of California at Berkeley Professor D. Seyferth Massachusetts Institute of Technology
Professor J. R. Etourneau Laboratoire de Chemie du Solide du C.N.R.S.
Dr. N. Sutin Brookhaven National Laboratory
Professor G. L. Geoffroy Pennsylvania State University
Professor R. A. Walton Purdue University
Professor L. S. Hegedus Colorado State University
Dr. J. H. Wernick Bell Laboratories xxvii
Contributors to Volume 6 Dr. Harmon B. Abrahamson Department of Chemistry University of North Dakota Grand Forks, N D 58202 (Sections 3.7.2.12 and 3.8.2.1.2)
Professor Paul Brandt Department of Chemistry and Physics Western Carolina University Cullowhee, NC 28723 (Sections 3.7.3.6 and 3.8.4)
Dr. Richard A. Catlow Davy Faraday Research Laboratory The Royal Institution 21 Abermarle St. London W1X 4BS England (Sections 3.10.1.2-3.10.1.2.3)
Professor Lawrence E. Conroy (deceased) Department of Chemistry 139 Smith Hall University of Minnesota Minneapolis, M N 55455 (Sections 3.10.2-3.10.2.1, 3.10.3.4.3, 3.10.3.5) Professor Peter Dorhout Department of Chemistry Colorado State Univeristy Ft. Collins, C O 80523-1872 (Sections 3.11.4-3.1 1.4.2, 3.11.5-3.1 1.5.2, 3.11.6-3.1 1.6.4.2, 3.11.7-3.11.7.2) Professor William Durfee Department of Chemistry Buffalo State College 1300 Elmwood Ave Buffalo, N Y 14222-1095
Dr. Anthony K. Cheetham Director, Materials Research Laboratory University of California at Santa Barbara Santa Barbara, CA 93106-5130 (Sections 3.10.1.5-3.10.1.5.5)
Dr. Katherine G. Fackler Chapman (formerly K. G. Fackler) 1775 Allen Dr. Geneva, IL 60134 (Sections 3.7.3-3.7.3.5.2, 3.8.3-3.8.3.5.2)
(Sections 3.7.2.1.3, 3.8.2-3.8.2.1.1, 3.8.2.1.3)
Professor Leroy Eyring Department of Chemistry Arizona State University Tempe. AZ 85287-1604 (Sections 3.10.2.2-3.10.2.2.3) Professor John P. Fackler, Jr. Department of Chemistry Texas A & M University College Station, TX77843 (Sections 3.7.3-3.7.3.5.2, 3.8.3-3.8.3.5.2) xxix
xxx
Contributors to Volume 6
Dr. Patrick K. Gallagher Department of Chemistry 120 West 18th Avenue, Box 180 Ohio State University Columbus, Ohio 43210 (Sections 3.10.2.3-3.10.2.3.5) Professor Martha Greenblatt Department of Chemistry P.O. Box 939 Rutgers University Piscataway, NJ 08855-0939 (Sections 3.10.3.2-3.10.3.3.5.5)
Professor Ram C. Mehrotra 41682 Jawahar Nagar Jaipur 302 0004 India (Sections 3.7.2.2-3.7.2.2.2, 3.7.2.4-3.7.2.5, 3.8.2.2-3.8.2.2.2, 3.8.2.4-3.8.2.4.3, 3.8.2.6-3.8.2.7.2, 3.8.2.10-3.8.2.10.1) Professor Arlan D. Norman Department of Chemistry University of Colorado Boulder, CO 80309-0215 (Sections 3.7-3.7.1, 3.8-3.8.1)
Mr. Erich Gundlach Department of Chemistry 120 West 18th Avenue, Box 180 Ohio State University Columbus, Ohio 43210
Professor Michael O’Keefe Department of Chemistry Arizona State University Tempe, AZ 85287-1604 (Sections 3.10-3.10.1.1.3)
Professor Dr. Emanuel Kaldis Laboratorium fur Festkorperphysik ETH Honiggerburg/HPF CH-8093 Zurich Switzerland (Sections 3.11-3.1 1.3.2)
Dr. Elizabeth M. Page Department of Chemistry University of Reading Whitenights, Reading RG6 2AD United Kingdom (Sections 3.7.4-3.7.4.7)
Professor Kenneth J. Klabunde Department of Chemistry Kansas State University Willard Hall Manhattan, KS 66506 (Sections 3.7.2.8, 3.7.3.7, 3.8.2.11-3.8.2.1 1.3, 3.8.3.7-3.8.3.7.2) Dr. Anton Lerf Walther Meissner Institut Walther Meissner Strasse 8 D-85748 Garching Germany (Sections 3.11.6-3.1 1.6.4.2)
Professor Michael T. Pope Department of Chemistry Georgetown University 37th and 0 Streets, N.W. Washington, DC 20057 (Sections 3.7.2.3-3.7.2.3.2, 3.7.2.6-3.7.2.7.2, 3.8.2.3-3.8.2.3.3, 3.8.2.5-3.8.2.5.3, 3.8.2.8-3.8.2.9.2) Professor Thomas B. Rauchfuss Department of Chemistry 550 S. Mathews Ave. University of Illinois Urbana-Champaign, IL 61801 (Sections 3.7.3.6, 3.8.3.6-3.8.3.6.3, 3.8.4)
Contributors to Volume 6
Professor B. Raveau Laboratory of Crystallographic Science and Materials ISMRA Universite de Caen Lab de Crystallographie 14032 Caen Cedex France Dr. Robert S. Roth National Institutes of Science and Technology Washington, DC 20234 (Sections 3.10.3.4-3.10.3.4.2)
Professor Dr. Bhim S. Saraswat Director, School of Sciences Indira Gandhi National Open University Maidan Garhu New Delhi - 110049 India (Sections 3.7.2.2-3.7.2.2.2, 3.7.2.4-3.7.2.5, 3.8.2.2-3.8.2.2.2, 3.8.2.4-3.8.2.4.3, 3.8.2.6-3.8.2.7.2, 3.8.2.10-3.8.2.10.1)
xxxi
Professor Hugo Steinfink Department of Chemistry University of Texas Austin, Texas 78712 (512) 471-5233 office (512) 471-7060 (Sections 3.11.4-3.11.4.1, 3.11.5-3.1 1.5.2, 3.11.7-3.1 1.7.2)
Professor Martin L. Thompson Department of Chemistry Lake Forest College Lake Forest, IL 60045 (Sections 3.9-3.9.4)
Dr. Richard J.D. Tilley School Engineering University of Cardiff P.O. Box 917 Cardiff CF2 1XH United Kingdom (Sections 3.10.1.3-3.10.1.4.2)
-
Inorganic Reactions and Methods Volume 6 ~~
~
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB
(0, S, Se, Te, Po)-Group IB (Cu, Ag, Au) or
IIB (Zn, Cd, Hg) Metal Bond 3.7.1 Introduction This section covers reactions by which bonds between the Group VIB elements (0, S, Se, Te and Po) and the Group IB (Cu, Ag and Au) or IIB (Zn, Cd and Hg) elements are formed. A large area of synthetic chemistry is represented, because bond formation of these types occurs in the contexts of inorganic, organometallic and materials chemistry. (A. D. NORMAN)
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.1 From Dioxygen and Ozone 3.7.2.1.1 By Reaction with the Metal
Copper metal reacts with O2 at red heat to form CuO. At still higher temperatures C u 2 0 forms. The oxides of Zn and Cd are prepared in similar manner, although they react rapidly with moist air. Hg and O2 react at temperatures of 350°C or higher. Ag and Au are resistant to attack by 0,; their oxides are prepared from various metal compounds. The most common oxides of the group IB and IIB metals are listed in Table 1. Those prepared by direct reaction with O2 are shown in boldface'-'. Colloidal suspensions of Ag in NaOH solutions react with dissolved O 3 forming Ago8. A g 2 0 is thought to be an intermediate. TABLE1. OXIDES OF GROUP IB
AND
cu
Zn ~~
~
C q O (high temperature) CuO (low temperature) Ag
AgZO, A g o
IIB METALS
~
ZnO Cd
CdO
Au
1
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.1 From Dioxygen and Ozone 3.7.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
2
Bond formation between group IB metal atoms and O 2 in low temperature adamantane matrices has been reportedg. An electron paramagnetic resonance study indicates that Cu forms a linear Cu(g1-O2)complex while both Ag and Au form side-on M(g2-02) structures. The reactivity of group IB'03" and IIB" metal surfaces with O2 and the structure and spectroscopy of the resulting oxide surface layers have been studied in ultrahigh vacuum. (W. S.DURFEE)
1. 2. 3. 4. 5. 6. 7.
8. 9. 10. 11. 12.
N. N . Greenwood, A. Earnshaw, Chemistry of the Elements, Pergamon Press, Oxford, 1984. B. Moody, Comparative Inorganic Chemistry, 3rd ed., Edward Arnold, London, 1991. F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. J. D. Lee, Concise Inorganic Chemistry, 5th ed., Chapman & Hall, London, 1996. A. G. Sharpe, Inorganic Chemistry, 3rd ed., Longman, Essex, 1992. P. A. Cox, Transition Metal Oxides: An Introduction to their Electronic Structure and Properties, Clarendon Press, Oxford, 1992. A. Wold, K. Dwight, Solid State Chemistry: Synthesis, Structure and Properties of Selected Oxides and Sulfides, Chapman & Hall, New York, 1993. P. Tissue, Polyhedron, 6, 1309 (1987). J. A. Howard, R. Sutcliffe, B. Mile, J . Phys. Chem., 88, 4351 (1984). C. Rehren, M . Muhler, X. Bao, Z . Phys. Chem., 174, 11 (1991). D. Herein, A. Nagy, R. Schlogl, Z. Phys. Chem., 197, 67 (1996). Z . Yougfa, S. Yangming, Surf. Sci.. 275, 357 (1992).
3.7.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
Reactions of dioxygen receive more attention than those of ozone; reactions of the latter produce primarily oxidized m e t a l ions and no metal-oxygen bonds. An exception is the formation of CuO by the action of ozone on weakly basic (pH 8-9) solutions of copper(I1) ion'. The chemistry of Group IB and IIB metals with dioxygen is dominated by copper. The ability to bind O2 to form characterizable complexes is limited to the 1' oxidation state. Even so, many reactions of dissolved copper species and oxygen lead to stoichiometric or catalytic oxidation of ligands or other substrates present in solution2. Use of simple salts such as CuCl in coordinating solvents such as pyridine leads to formation of copper-oxygen adducts3s4: 2cuc1
+ o.502
Cucl2
+ Cuo
(a)
which are stable only in solution. Thought to be -[Cu-O-Inpolymers stabilized by pyridine coordination4, these compounds decompose to normal CuO upon attempted isolation3.Anionic salts with a 1 : 1 Cu: O 2 stoichiometry appear to be stable in the solid state5 and even exhibit reversible binding: ( ~ h o l i n e[Cu(SnCl3),,Cl4-,] )~
ec
(~holine)~[Cu(SnCl~),,Cl~-~(O~)], n = 1, 2, 3,4 (b)
Macrocycles and chelates seem to improve the oxygen-binding ability of copper(1). Tetraazamacrocyle-Cu(1) complexes react with dioxygen by an addition mechanism6,
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.1 From Dioxygen and Ozone 3.7.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
2
Bond formation between group IB metal atoms and O 2 in low temperature adamantane matrices has been reportedg. An electron paramagnetic resonance study indicates that Cu forms a linear Cu(g1-O2)complex while both Ag and Au form side-on M(g2-02) structures. The reactivity of group IB'03" and IIB" metal surfaces with O2 and the structure and spectroscopy of the resulting oxide surface layers have been studied in ultrahigh vacuum. (W. S.DURFEE)
1. 2. 3. 4. 5. 6. 7.
8. 9. 10. 11. 12.
N. N . Greenwood, A. Earnshaw, Chemistry of the Elements, Pergamon Press, Oxford, 1984. B. Moody, Comparative Inorganic Chemistry, 3rd ed., Edward Arnold, London, 1991. F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. J. D. Lee, Concise Inorganic Chemistry, 5th ed., Chapman & Hall, London, 1996. A. G. Sharpe, Inorganic Chemistry, 3rd ed., Longman, Essex, 1992. P. A. Cox, Transition Metal Oxides: An Introduction to their Electronic Structure and Properties, Clarendon Press, Oxford, 1992. A. Wold, K. Dwight, Solid State Chemistry: Synthesis, Structure and Properties of Selected Oxides and Sulfides, Chapman & Hall, New York, 1993. P. Tissue, Polyhedron, 6, 1309 (1987). J. A. Howard, R. Sutcliffe, B. Mile, J . Phys. Chem., 88, 4351 (1984). C. Rehren, M . Muhler, X. Bao, Z . Phys. Chem., 174, 11 (1991). D. Herein, A. Nagy, R. Schlogl, Z. Phys. Chem., 197, 67 (1996). Z . Yougfa, S. Yangming, Surf. Sci.. 275, 357 (1992).
3.7.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
Reactions of dioxygen receive more attention than those of ozone; reactions of the latter produce primarily oxidized m e t a l ions and no metal-oxygen bonds. An exception is the formation of CuO by the action of ozone on weakly basic (pH 8-9) solutions of copper(I1) ion'. The chemistry of Group IB and IIB metals with dioxygen is dominated by copper. The ability to bind O2 to form characterizable complexes is limited to the 1' oxidation state. Even so, many reactions of dissolved copper species and oxygen lead to stoichiometric or catalytic oxidation of ligands or other substrates present in solution2. Use of simple salts such as CuCl in coordinating solvents such as pyridine leads to formation of copper-oxygen adducts3s4: 2cuc1
+ o.502
Cucl2
+ Cuo
(a)
which are stable only in solution. Thought to be -[Cu-O-Inpolymers stabilized by pyridine coordination4, these compounds decompose to normal CuO upon attempted isolation3.Anionic salts with a 1 : 1 Cu: O 2 stoichiometry appear to be stable in the solid state5 and even exhibit reversible binding: ( ~ h o l i n e[Cu(SnCl3),,Cl4-,] )~
ec
(~holine)~[Cu(SnCl~),,Cl~-~(O~)], n = 1, 2, 3,4 (b)
Macrocycles and chelates seem to improve the oxygen-binding ability of copper(1). Tetraazamacrocyle-Cu(1) complexes react with dioxygen by an addition mechanism6,
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.1 From Dioxygen and Ozone 3.7.2.1.3 By Insertion into Metal-Ligand Bonds
3
but the products are not fully characterized. Tripyrazolylboratocopper(1) is a ligandbridged dimer that binds one molecule of dioxygen per dimer’ when dissolved in nonprotic solvents. A tricyclic ligand with two N2S20 coordination sites binds two copper(1)ions’. This dication then binds one oxygen per two copper atoms, presumably through Cu-00-Cu binding. These dimeric complexes serve as model systems for the reversible binding of oxygen by hemocyaning. Dioxygen binds to a two-copper active site” in a p-peroxo (Cu-00-Cu) fashion’’. Polymers based on chelating glyoxime units coordinating copper(1) also reversibly bind molecular ~ x y g e n ” , ’ ~ . Another well-characterized reaction is that of an organocadmium species at low temperat~re’~. CdEt2
+202
- 40‘C
CdEt2. 2 0 2
-
Cd(O0Et)Z
Irreversible decomposition to the peroxoethyl compound is accelerated by warming or addition of other ligands.
(H.B. ABRAHAMSON) 1. A. F. Chudnov, J . Gen. Chem. USSR, 44, 1207 (1974). 2. A. D. Zuberbiihler, in Metal Ions in Biological Systems, Vol. 5, H. Sigel, ed., Dekker, New York, 1976, p. 325. 3. C. E. Kramer, G. Davies, R. L. Davis, R. W. Slaven, J . Chem. Soc., Chem. Commun., 606 (1975). 4. I. Bodek, G. Davies, Inorg. Chim. Acta, 27, 213 (1978). 5. M. Brezeanu, I. Jitaru, Rec. Roum. Chim., 17, 1857 (1972). 6. A. M. Tait, M. Z. Hoffman, E. Haynon, Inorg. Chem., 15, 934 (1976). 7. C. S. Arcus, J. L. Wilkinson, C. Mealli,T. J. Marks, J. A. Ibers, J . Am. Chem. Soc., 96,7564(1974). 8. R. Louis, Y. Agnus, R. Weiss, J . Am. Chem. Soc., 100, 3604 (1978). 9. I. Pecht, 0. Farver, M. Goldberg, Ado. Chem. Ser., 162, 177 (1977). 10. A. G. Lappin, in Inorganic Reaction Mechanisms, Vol. 7, A. G. Sykes, ed., Royal Society of Chemistry, Cambridge, 1981, p. 354. 11. R. S. Himmelwright, N. C. Eickman, E. I. Solomon, J . Am. Chem. Soc., I O I , 1576 (1979). 12. S. J. Kim, T. Takizawa, Makromol. Chem., 176, 891 (1975). 13. H. Yukimasa, H. Sawai, T. Takizama, Makromol. Chem., 180, 1681 (1979). 14. Yu. A. Alexandrov, G. N. Figurova, G. A. Razuvaev, J . Organomet. Chem., 57, 71 (1973). 3.7.2.1.3 By Insertion into Metal-Ligand Bonds
Insertion of oxygen into group I and IIB metal-ligand bonds, where either O2 or O 3 is the oxygen source, is limited to metal-carbon bonds in dialkyl complexes’. Zinc(I1) dialkyl complexes react with 0’ to form stable alkylperoxide complexes that ultimately rearrange to zinc(I1) dialkoxides’. R2Zn
-
+ O2
-
RZnOOR-
ROZnOR
(a)
Dialkylcadmium complexes form stable alkylperoxide and bis(alky1peroxide) specie~~. RCdOOR + ROOOCdOOR R’Cd + 0’ (b) Diallylmercury reacts with singlet O2 to the bis(allylperoxide)s4.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.1 From Dioxygen and Ozone 3.7.2.1.3 By Insertion into Metal-Ligand Bonds
3
but the products are not fully characterized. Tripyrazolylboratocopper(1) is a ligandbridged dimer that binds one molecule of dioxygen per dimer’ when dissolved in nonprotic solvents. A tricyclic ligand with two N2S20 coordination sites binds two copper(1)ions’. This dication then binds one oxygen per two copper atoms, presumably through Cu-00-Cu binding. These dimeric complexes serve as model systems for the reversible binding of oxygen by hemocyaning. Dioxygen binds to a two-copper active site” in a p-peroxo (Cu-00-Cu) fashion’’. Polymers based on chelating glyoxime units coordinating copper(1) also reversibly bind molecular ~ x y g e n ” , ’ ~ . Another well-characterized reaction is that of an organocadmium species at low temperat~re’~. CdEt2
+202
- 40‘C
CdEt2. 2 0 2
-
Cd(O0Et)Z
Irreversible decomposition to the peroxoethyl compound is accelerated by warming or addition of other ligands.
(H.B. ABRAHAMSON) 1. A. F. Chudnov, J . Gen. Chem. USSR, 44, 1207 (1974). 2. A. D. Zuberbiihler, in Metal Ions in Biological Systems, Vol. 5, H. Sigel, ed., Dekker, New York, 1976, p. 325. 3. C. E. Kramer, G. Davies, R. L. Davis, R. W. Slaven, J . Chem. Soc., Chem. Commun., 606 (1975). 4. I. Bodek, G. Davies, Inorg. Chim. Acta, 27, 213 (1978). 5. M. Brezeanu, I. Jitaru, Rec. Roum. Chim., 17, 1857 (1972). 6. A. M. Tait, M. Z. Hoffman, E. Haynon, Inorg. Chem., 15, 934 (1976). 7. C. S. Arcus, J. L. Wilkinson, C. Mealli,T. J. Marks, J. A. Ibers, J . Am. Chem. Soc., 96,7564(1974). 8. R. Louis, Y. Agnus, R. Weiss, J . Am. Chem. Soc., 100, 3604 (1978). 9. I. Pecht, 0. Farver, M. Goldberg, Ado. Chem. Ser., 162, 177 (1977). 10. A. G. Lappin, in Inorganic Reaction Mechanisms, Vol. 7, A. G. Sykes, ed., Royal Society of Chemistry, Cambridge, 1981, p. 354. 11. R. S. Himmelwright, N. C. Eickman, E. I. Solomon, J . Am. Chem. Soc., I O I , 1576 (1979). 12. S. J. Kim, T. Takizawa, Makromol. Chem., 176, 891 (1975). 13. H. Yukimasa, H. Sawai, T. Takizama, Makromol. Chem., 180, 1681 (1979). 14. Yu. A. Alexandrov, G. N. Figurova, G. A. Razuvaev, J . Organomet. Chem., 57, 71 (1973). 3.7.2.1.3 By Insertion into Metal-Ligand Bonds
Insertion of oxygen into group I and IIB metal-ligand bonds, where either O2 or O 3 is the oxygen source, is limited to metal-carbon bonds in dialkyl complexes’. Zinc(I1) dialkyl complexes react with 0’ to form stable alkylperoxide complexes that ultimately rearrange to zinc(I1) dialkoxides’. R2Zn
-
+ O2
-
RZnOOR-
ROZnOR
(a)
Dialkylcadmium complexes form stable alkylperoxide and bis(alky1peroxide) specie~~. RCdOOR + ROOOCdOOR R’Cd + 0’ (b) Diallylmercury reacts with singlet O2 to the bis(allylperoxide)s4.
4
3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.2 From Water and Alcohols 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
Dialkylmercury complexes react with O2 forming alkylperoxides that rearrange to form mercury alkoxides. Several mechanisms have been suggested, all of which involve radical intermediates Oxygen insertions during heterogeneous oxidation on metal oxide surfaces have been discussed, such as in the oxidation of propene on CuzO surfaces' and ethene on Ag surfaces8. 16.
(W. S.DURFEE) 1. T. G. Brilkina, V. A. Shushunov, Reactions of Organometallic Componds with Oxygen and Peroxides, Iliffe, London, 1969. 2. G. Sosnowsky, J. H. Brown, Chem. Rev., 66, 529 (1966). 3. Y . A. Alexandrov, S. A. Lebedev,N. V. Kuznetsova, G. A. Razuvaev, J . Organomet. Chem., 177,91 (1979). 4. H. S. Dang, A. G. Davies, J . Organomet. Chem., 430, 287 (1992). 5. F. R. Jensen, D. Heyman, J . Am. Chern. SOC.,88, 3438 (1966). 6. K. C. Bass, Organornet. Chem. Rev., I , 391 (1966). 7 . K. H. Shulz, D. F. Cox, J . Catal., 143, 464 (1993). 8. V. I. Bukhtiyarov, I. P. Prosvirin, R. I. Kvon, Surf Sci., 320, L47 (1994).
3.7.2.2 From Water and Alcohols 3.7.2.2.1 By Reactions with Elements
Of the coinage metals, Cu reacts reversibly at dull red heat with H 2 0 vapor to yield CuzO and H z gas': (a) ~ C UHzO CUZO H2
+
+
Highly purified Zn does not react even when boiled with H 2 0 for a long time, but in the presence of traces of Fe, As, or Sb, Zn decomposes boiling H z O to liberate HZ2: Zn
+ H,O-
ZnO
+ Hz
(b)
When steam is passed over Zn or Cd at dull red heat, H z is evolved and metal oxides' are formed. (R. C.MEHROTRA, 6.S. SARASWAT)
1. J. W. Laist, in Comprehensive Inorganic Chemistry. Vol. 11, M. C. Sneed, J. L. Maynard, R. C. Brasted, eds., Van Nostrand, New York, 1954, p. 62. 2. J. W. Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. IV, Longmans, London, 1960, p. 474. 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
(i) From H,O. The blue aquo ion [Cu(H20),J2+, formed on dissolving Cu(I1) salts in excess of H 2 0 , behaves like a mild acid':
+
[ C U ( H ~ O ) ~ ] ~H' 2 0 + [Cu(H,O),OH]'
+ H,O+
(a)
The aquo ions of Zn, Cd, and Hg are also strong acids, and aqueous solutions of their salts undergo extensive hydrolysis'. In perchlorate solutions (below 0.1 M), the only species for Zn and Cd are the [MOH]' ions3, e.g.: M"(aq)
+ H 2 0=$MOH+(aq) + H'
(b)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
4
3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.2 From Water and Alcohols 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
Dialkylmercury complexes react with O2 forming alkylperoxides that rearrange to form mercury alkoxides. Several mechanisms have been suggested, all of which involve radical intermediates Oxygen insertions during heterogeneous oxidation on metal oxide surfaces have been discussed, such as in the oxidation of propene on CuzO surfaces' and ethene on Ag surfaces8. 16.
(W. S.DURFEE) 1. T. G. Brilkina, V. A. Shushunov, Reactions of Organometallic Componds with Oxygen and Peroxides, Iliffe, London, 1969. 2. G. Sosnowsky, J. H. Brown, Chem. Rev., 66, 529 (1966). 3. Y . A. Alexandrov, S. A. Lebedev,N. V. Kuznetsova, G. A. Razuvaev, J . Organomet. Chem., 177,91 (1979). 4. H. S. Dang, A. G. Davies, J . Organomet. Chem., 430, 287 (1992). 5. F. R. Jensen, D. Heyman, J . Am. Chern. SOC.,88, 3438 (1966). 6. K. C. Bass, Organornet. Chem. Rev., I , 391 (1966). 7 . K. H. Shulz, D. F. Cox, J . Catal., 143, 464 (1993). 8. V. I. Bukhtiyarov, I. P. Prosvirin, R. I. Kvon, Surf Sci., 320, L47 (1994).
3.7.2.2 From Water and Alcohols 3.7.2.2.1 By Reactions with Elements
Of the coinage metals, Cu reacts reversibly at dull red heat with H 2 0 vapor to yield CuzO and H z gas': (a) ~ C UHzO CUZO H2
+
+
Highly purified Zn does not react even when boiled with H 2 0 for a long time, but in the presence of traces of Fe, As, or Sb, Zn decomposes boiling H z O to liberate HZ2: Zn
+ H,O-
ZnO
+ Hz
(b)
When steam is passed over Zn or Cd at dull red heat, H z is evolved and metal oxides' are formed. (R. C.MEHROTRA, 6.S. SARASWAT)
1. J. W. Laist, in Comprehensive Inorganic Chemistry. Vol. 11, M. C. Sneed, J. L. Maynard, R. C. Brasted, eds., Van Nostrand, New York, 1954, p. 62. 2. J. W. Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. IV, Longmans, London, 1960, p. 474. 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
(i) From H,O. The blue aquo ion [Cu(H20),J2+, formed on dissolving Cu(I1) salts in excess of H 2 0 , behaves like a mild acid':
+
[ C U ( H ~ O ) ~ ] ~H' 2 0 + [Cu(H,O),OH]'
+ H,O+
(a)
The aquo ions of Zn, Cd, and Hg are also strong acids, and aqueous solutions of their salts undergo extensive hydrolysis'. In perchlorate solutions (below 0.1 M), the only species for Zn and Cd are the [MOH]' ions3, e.g.: M"(aq)
+ H 2 0=$MOH+(aq) + H'
(b)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
4
3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.2 From Water and Alcohols 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
Dialkylmercury complexes react with O2 forming alkylperoxides that rearrange to form mercury alkoxides. Several mechanisms have been suggested, all of which involve radical intermediates Oxygen insertions during heterogeneous oxidation on metal oxide surfaces have been discussed, such as in the oxidation of propene on CuzO surfaces' and ethene on Ag surfaces8. 16.
(W. S.DURFEE) 1. T. G. Brilkina, V. A. Shushunov, Reactions of Organometallic Componds with Oxygen and Peroxides, Iliffe, London, 1969. 2. G. Sosnowsky, J. H. Brown, Chem. Rev., 66, 529 (1966). 3. Y . A. Alexandrov, S. A. Lebedev,N. V. Kuznetsova, G. A. Razuvaev, J . Organomet. Chem., 177,91 (1979). 4. H. S. Dang, A. G. Davies, J . Organomet. Chem., 430, 287 (1992). 5. F. R. Jensen, D. Heyman, J . Am. Chern. SOC.,88, 3438 (1966). 6. K. C. Bass, Organornet. Chem. Rev., I , 391 (1966). 7 . K. H. Shulz, D. F. Cox, J . Catal., 143, 464 (1993). 8. V. I. Bukhtiyarov, I. P. Prosvirin, R. I. Kvon, Surf Sci., 320, L47 (1994).
3.7.2.2 From Water and Alcohols 3.7.2.2.1 By Reactions with Elements
Of the coinage metals, Cu reacts reversibly at dull red heat with H 2 0 vapor to yield CuzO and H z gas': (a) ~ C UHzO CUZO H2
+
+
Highly purified Zn does not react even when boiled with H 2 0 for a long time, but in the presence of traces of Fe, As, or Sb, Zn decomposes boiling H z O to liberate HZ2: Zn
+ H,O-
ZnO
+ Hz
(b)
When steam is passed over Zn or Cd at dull red heat, H z is evolved and metal oxides' are formed. (R. C.MEHROTRA, 6.S. SARASWAT)
1. J. W. Laist, in Comprehensive Inorganic Chemistry. Vol. 11, M. C. Sneed, J. L. Maynard, R. C. Brasted, eds., Van Nostrand, New York, 1954, p. 62. 2. J. W. Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. IV, Longmans, London, 1960, p. 474. 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
(i) From H,O. The blue aquo ion [Cu(H20),J2+, formed on dissolving Cu(I1) salts in excess of H 2 0 , behaves like a mild acid':
+
[ C U ( H ~ O ) ~ ] ~H' 2 0 + [Cu(H,O),OH]'
+ H,O+
(a)
The aquo ions of Zn, Cd, and Hg are also strong acids, and aqueous solutions of their salts undergo extensive hydrolysis'. In perchlorate solutions (below 0.1 M), the only species for Zn and Cd are the [MOH]' ions3, e.g.: M"(aq)
+ H 2 0=$MOH+(aq) + H'
(b)
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.2 From Water and Alcohols 3.7.2.2.2 By Hydrolysis or Alcoholysis of Metal-Ligand Bonds
5
For more concentrated Cd solutions, however, the principal species is [CdzOH] '+:
+
2Cd2+(aq) H 2 0e [Cd20H]3'(aq)
+ H+
(c)
The hydrate ZnC12.4Hz0is liquid at RT and behaves as a strong protic acid4. Although no Hg(OH)z is isolated, the hydrolysis of Hg2' ion in perchlorate solution is interpreted in terms of the equilibria5:
+ Ht + H z 0 e Hg(0H)Z + H +
Hg2+ + HzO+HgOH+ HgOH'
(4 (4
In aqueous solution, mercury(I1) halides exist ca. 99% as HgX2 molecules, but some hydrolysis occurs, and the principal equilibrium is3
+ H20+HgOHX + H + + X-
HgXz
(f
1
By contrast, HgzF2 is hydrolyzed to give Hg06:
In E t 2 0 at RT, MeHgN(SiMe& is similarly hydrolyzed to yield (MeHg),07: 2MeHgN(SiMe3),
+ HzO-
(MeHg),O
The hydrolysis of Et2Zn at 0°C yields (EtZnOH)28:
+ HzO-
2Et2Zn
(EtZnOH)z
+ 2(Me3S&NH
+XzH6
(i)
(j)
( i i ) From ROH. Reaction of CuPh with a small excess of PhOH in anhydrous E t 2 0 at RT under dry N2 yields CuOPhg:
CuPh
+ PhOH-
CuOPh
+ C6H6
(k)
Alcoholysis of CuMe in E t 2 0 in dry Nz, however, occurs even at O'C, resulting in the formation of CuOR": CuMe (R
=
+ ROH-
CuOR
+ CH4
(1)
Me, n-Bu, s-Bu, t-Bu, cyclohexyl, Ph)
Alcoholysis of Me2M (M = Zn and Cd) compounds in n-hexane or benzene between - 78 and 40°C yields (MeMOR), specie^"-'^: 4MezZn + 4ROH-
(MeZnOR),
+ 4CH4
(4
(R = Me, Et, i-Pr, t-Bu, Ph) 4Me2Cd
+ 4ROH-
(MeCdOR)4 + 4CH4
(4
The reaction of MezZn with excess primary and secondary alcohols in C6H6 at 70-80"C, however, yields Zn(OR), 14: MezZn
+ 2ROH-
Zn(OR)2
+ 2CH4
(R = Me, Et, i-Pr, n-C12H25)
(0)
6
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.3 From Hydrogen Peroxide and Organic Peroxides 3.7.2.3.1 By Oxidation of the Metals and Their Complexes
Although the reaction of Ph,Zn with t-BuOH at 70°C in C6H6 yields Zn(0Bu-t),, Me2Zn even under these conditions forms only Mez110Bu-t’~. Toward a given alcohol, the R,Zn compounds are more reactive than the RzCd compounds and the reactivity follows the order: Et,Zn > Et,Cd > Me2Cd”. Reaction of ArzHg with C6C150H in refluxing xylene yields ArHgOC6C15’6:
(R. C.MEHROTRA, B. S. SARASWAT)
D. Nicholls, Complexes and First Row Transition Elements, Macmillan, London, 1979, p. 202. D. D. Perrin, J . Chem. Soc., 4500 (1962). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. D. H. McDaniel, Inorg. Chem., 18, 1412 (1979). R. D. Hancock, F. Marsicano, J . Chem. Soc., Dalton Trans., 1832 (1976). J. D. Lee, Concise Inorganic Chemistry, 4th ed., Chapman & Hall, London, 1991, p. 846. J. Lorberth, F. Weller, J . Organomet. Chem., 32, 145 (1971). R. J. Harold, S. L. Aggarwal, V. Neff, Can. J . Chem., 41, 1368 (1963). T. Kawaki, H. Hashimoto, Bull. Chem. Soc. Jpn., 45, 1499 (1972). G. Gosta, A. Camus, N. Marsich, J . Inorg. Nucl. Chem., 27, 281 (1965); G. M. Whitesides, J. S. Sadowski, J. Lilburn, J . Am. Chem. Soc., 96, 2829 (1976). 11. G. E. Coates, K. Wade, Organometallic Compounds, Vol. 1, 3rd ed., Methuen, London, 1967, p. 134. 12. G. E. Coates, D. Ridley, J . Chem. Soc., 1870 (1965); G. E. Coates, P. D. Roberts, J . Chem. Soc., A , 1233 (1967). 13. G. E. Coates, A. Lauder, J . Chem. Soc., A , 264 (1966). 14. J. M. Bruce, B. C. Cutsforth, D. W. Farren, F. G. Hutchinson, F. M. Rabagliati, D. R. Reed, J . Chem. Soc., B, 799, 1020 (1966). 15. A. Deffieux, M. Sepulchre, N. Spassky, J . Organomet. Chem., 80, 311 (1974). 16. G. Leandri, D. Spinelli, A. Salvemini, Ann. Chim., 50, 1046 (1960).
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
3.7.2.3 From Hydrogen Peroxide and Organic Peroxides 3.7.2.3.1 By Oxidation of the Metals and Their Complexes
Metallic Cu, Ag, Au, and Hg are all efficient heterogeneous catalysts for the decomposition of H 2 0 2 ;Zn and Cd are slightly less so. Consequently there have been few investigations directed toward stoichiometric reaction of these metals with H 2 0 2 and organic peroxides. Metallic Zn is converted to ZnO upon treatment with neutral H 2 0 2 . Dissolution of Cu, Ag, and Hg yields aquocations of Cu(II), Ag(I), and Hg(I1); reaction occurs in 30% H 2 0 2acidified with dilute H2S04 (Cu, Ag) and HOAc (Cu, Ag, Hg)’. It is postulated that [Cu(bipy),] reacts with H 2 0 2 to give, initially, [Cu(bipy),O] ’+, Dialkyl and diary1 compounds of Cd and Hg react with ROOH, RCOOH, and (RCOO), yielding peroxo, alkoxo, or carboxylato derivative^^,^. Corresponding reactions with R,Zn are not documented. With R;Cd ( R = Me, Et, Bu-n, Ph), reactions with ROOH (R = Bu-t, CI0Hz1,cumyl) proceed at RT forming R’CdOOR or Cd(OOR),. Diperoxo compounds are converted to Cd(OR)2 upon heating above 60°C. (Caution: Fast heating of Cd(OOBu-Qzto 100°C results in explosion). Corresponding reactions with R2Hg or PhHgCl occur at higher temperatures and yield a mixture of mercury alkoxides and metallic Hg through a free radical mechanism; e.g., the following reactions occur in +
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
6
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.3 From Hydrogen Peroxide and Organic Peroxides 3.7.2.3.1 By Oxidation of the Metals and Their Complexes
Although the reaction of Ph,Zn with t-BuOH at 70°C in C6H6 yields Zn(0Bu-t),, Me2Zn even under these conditions forms only Mez110Bu-t’~. Toward a given alcohol, the R,Zn compounds are more reactive than the RzCd compounds and the reactivity follows the order: Et,Zn > Et,Cd > Me2Cd”. Reaction of ArzHg with C6C150H in refluxing xylene yields ArHgOC6C15’6:
(R. C.MEHROTRA, B. S. SARASWAT)
D. Nicholls, Complexes and First Row Transition Elements, Macmillan, London, 1979, p. 202. D. D. Perrin, J . Chem. Soc., 4500 (1962). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. D. H. McDaniel, Inorg. Chem., 18, 1412 (1979). R. D. Hancock, F. Marsicano, J . Chem. Soc., Dalton Trans., 1832 (1976). J. D. Lee, Concise Inorganic Chemistry, 4th ed., Chapman & Hall, London, 1991, p. 846. J. Lorberth, F. Weller, J . Organomet. Chem., 32, 145 (1971). R. J. Harold, S. L. Aggarwal, V. Neff, Can. J . Chem., 41, 1368 (1963). T. Kawaki, H. Hashimoto, Bull. Chem. Soc. Jpn., 45, 1499 (1972). G. Gosta, A. Camus, N. Marsich, J . Inorg. Nucl. Chem., 27, 281 (1965); G. M. Whitesides, J. S. Sadowski, J. Lilburn, J . Am. Chem. Soc., 96, 2829 (1976). 11. G. E. Coates, K. Wade, Organometallic Compounds, Vol. 1, 3rd ed., Methuen, London, 1967, p. 134. 12. G. E. Coates, D. Ridley, J . Chem. Soc., 1870 (1965); G. E. Coates, P. D. Roberts, J . Chem. Soc., A , 1233 (1967). 13. G. E. Coates, A. Lauder, J . Chem. Soc., A , 264 (1966). 14. J. M. Bruce, B. C. Cutsforth, D. W. Farren, F. G. Hutchinson, F. M. Rabagliati, D. R. Reed, J . Chem. Soc., B, 799, 1020 (1966). 15. A. Deffieux, M. Sepulchre, N. Spassky, J . Organomet. Chem., 80, 311 (1974). 16. G. Leandri, D. Spinelli, A. Salvemini, Ann. Chim., 50, 1046 (1960).
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
3.7.2.3 From Hydrogen Peroxide and Organic Peroxides 3.7.2.3.1 By Oxidation of the Metals and Their Complexes
Metallic Cu, Ag, Au, and Hg are all efficient heterogeneous catalysts for the decomposition of H 2 0 2 ;Zn and Cd are slightly less so. Consequently there have been few investigations directed toward stoichiometric reaction of these metals with H 2 0 2 and organic peroxides. Metallic Zn is converted to ZnO upon treatment with neutral H 2 0 2 . Dissolution of Cu, Ag, and Hg yields aquocations of Cu(II), Ag(I), and Hg(I1); reaction occurs in 30% H 2 0 2acidified with dilute H2S04 (Cu, Ag) and HOAc (Cu, Ag, Hg)’. It is postulated that [Cu(bipy),] reacts with H 2 0 2 to give, initially, [Cu(bipy),O] ’+, Dialkyl and diary1 compounds of Cd and Hg react with ROOH, RCOOH, and (RCOO), yielding peroxo, alkoxo, or carboxylato derivative^^,^. Corresponding reactions with R,Zn are not documented. With R;Cd ( R = Me, Et, Bu-n, Ph), reactions with ROOH (R = Bu-t, CI0Hz1,cumyl) proceed at RT forming R’CdOOR or Cd(OOR),. Diperoxo compounds are converted to Cd(OR)2 upon heating above 60°C. (Caution: Fast heating of Cd(OOBu-Qzto 100°C results in explosion). Corresponding reactions with R2Hg or PhHgCl occur at higher temperatures and yield a mixture of mercury alkoxides and metallic Hg through a free radical mechanism; e.g., the following reactions occur in +
7 3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.4 From Neutral Oxygen Donor Ligands 3.7.2.4.1 By Ligand Displacement Reactions with Transition Metal Complexes
benzene at 70°C: (i-C3H7)2Hg + t-C4H90H(C3H7)zHg
+ C3H7HgOOC4H9
-
C3Hs
+ (i-C,H,)HgOO(t-C,Hg)
C3H7HgOC4H9
+ C3H7HgOC3H7
(a) (b)
The R,Cd compounds are more reactive than R2Hg, alkyls are more reactive than aryls, and ( R C 0 0 ) 2 are more reactive than ROOH. (M. T. POPE)
1. W. C. Schumb, C. N. Satterfield, R. L. Wentworth, Hydrogen Peroxide, Reinhold, New York, 1955. 2. N. V. Gorbunov, A. P. Purmal, Y. I. Skurlatov, Russ. J . Phys. Chem. (Engl. tranl.), 49,1169 (1975). 3. T. G. Brilkina, V. A. Shushunov, Reactions of Organometallic Compounds with Oxygen and Peroxides, Iliffe, London, 1969. 4. G. A. Razuvaev, V. A. Shushunov, V. A. Dodonov, T. G. Brilkina, Organic Peroxides, Vol. 3, D. Swern, ed., Wiley-Interscience, New York, 1972, p. 141. 3.7.2.3.2 By Oxidation of the Ligands Coordinated to the Metals
Phthalocyanines of Cu, Ag, Zn, and Hg are oxidized to the aquo or sulfato complexes, phthalimide, and ammonium ion by H 2 0 z in 17 M HzSO4l. (M. T. POPE)
1. B. D. Berezin, G. V. Sennikova, Kinet. Catal. (Engl. transl.), 9, 437 (1968).
3.7.2.4 From Neutral Oxygen Donor Ligands [Ethers, Aldehydes, Ketones, Pyridine N-Oxides, Phosphine Oxides, Arsine Oxides, and Dialkyl(ary1) Sulfoxides] 3.7.2.4.1 By Ligand Displacement Reactions with Transition Metal Complexes
(i) From Ethers. Although T H F reacts with ZnC1, and M[Hg(SCN),][M = Cu(I1) and Zn(II)] to yield the neutral adducts ZnCl,. 2THF and M[Hg(SCN),]. 2THF, respectively, it replaces the weak donor MeCN from [M(MeCN)6](SbC16), to form the sohates [CU(THF)6](SbCl& .2THF and [Zn(THF)6](SbC16)2,respectively'. (ii) From Ketones. Complexes of Cu(II), Ag(I), Au(III), Zn(II), Cd(II), and Hg(I1) with ketones are not known. However, spectroscopic studies in CH2C12 solution give evidence for the formation of [AgL,]BF4 (L = MeCOEt, Et,CO, MeCOPh, p-MeC6H4COMe, and p-C1C6H4COMe) and a solid complex [Ag(pMeC6H4COMe),]BF4 is isolated by cooling the CH2C12solution of the reactants2.
(iii) From py0, &PO, and R3As0. Reactions of CuX, (X = C1, Br, and I) with p y 0 and other heterocyclic amine N-oxides result in the formation of neutral dimeric complexes, [CuX,. P ~ O ] , In ~ .the reactions of Cu(C104), and Cu(BF4), with py0, however, ionic complexes, [Cu(pyO),](ClO,), and [Cu(pyO),](BF,), form4. Similarly, the reaction of Hg(C104)2 with p y o yields [Hg(pyO)6](C104),'. Reactions of R 3 P 0 and R 3 A s 0 with MX2 yield simple adducts, MX2.2R3E0 (M = C u , X = C 1 a n d B r , R = P h , E = P a n d A s 6 ; M = Z n , C d , a n d H g , X = C 1 , R = P h , E = P'). However, in the presence of noncoordinating ligands, C10, and R e 0 4 , ionic complexes, [ C U ( M ~ ~ E O ) ~ ( C ~ O ~ (E ) ] (=CP~ and O ~ )As)8, [Cu(Ph,EO),(ReO,)] (Re04)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
7 3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.4 From Neutral Oxygen Donor Ligands 3.7.2.4.1 By Ligand Displacement Reactions with Transition Metal Complexes
benzene at 70°C: (i-C3H7)2Hg + t-C4H90H(C3H7)zHg
+ C3H7HgOOC4H9
-
C3Hs
+ (i-C,H,)HgOO(t-C,Hg)
C3H7HgOC4H9
+ C3H7HgOC3H7
(a) (b)
The R,Cd compounds are more reactive than R2Hg, alkyls are more reactive than aryls, and ( R C 0 0 ) 2 are more reactive than ROOH. (M. T. POPE)
1. W. C. Schumb, C. N. Satterfield, R. L. Wentworth, Hydrogen Peroxide, Reinhold, New York, 1955. 2. N. V. Gorbunov, A. P. Purmal, Y. I. Skurlatov, Russ. J . Phys. Chem. (Engl. tranl.), 49,1169 (1975). 3. T. G. Brilkina, V. A. Shushunov, Reactions of Organometallic Compounds with Oxygen and Peroxides, Iliffe, London, 1969. 4. G. A. Razuvaev, V. A. Shushunov, V. A. Dodonov, T. G. Brilkina, Organic Peroxides, Vol. 3, D. Swern, ed., Wiley-Interscience, New York, 1972, p. 141. 3.7.2.3.2 By Oxidation of the Ligands Coordinated to the Metals
Phthalocyanines of Cu, Ag, Zn, and Hg are oxidized to the aquo or sulfato complexes, phthalimide, and ammonium ion by H 2 0 z in 17 M HzSO4l. (M. T. POPE)
1. B. D. Berezin, G. V. Sennikova, Kinet. Catal. (Engl. transl.), 9, 437 (1968).
3.7.2.4 From Neutral Oxygen Donor Ligands [Ethers, Aldehydes, Ketones, Pyridine N-Oxides, Phosphine Oxides, Arsine Oxides, and Dialkyl(ary1) Sulfoxides] 3.7.2.4.1 By Ligand Displacement Reactions with Transition Metal Complexes
(i) From Ethers. Although T H F reacts with ZnC1, and M[Hg(SCN),][M = Cu(I1) and Zn(II)] to yield the neutral adducts ZnCl,. 2THF and M[Hg(SCN),]. 2THF, respectively, it replaces the weak donor MeCN from [M(MeCN)6](SbC16), to form the sohates [CU(THF)6](SbCl& .2THF and [Zn(THF)6](SbC16)2,respectively'. (ii) From Ketones. Complexes of Cu(II), Ag(I), Au(III), Zn(II), Cd(II), and Hg(I1) with ketones are not known. However, spectroscopic studies in CH2C12 solution give evidence for the formation of [AgL,]BF4 (L = MeCOEt, Et,CO, MeCOPh, p-MeC6H4COMe, and p-C1C6H4COMe) and a solid complex [Ag(pMeC6H4COMe),]BF4 is isolated by cooling the CH2C12solution of the reactants2.
(iii) From py0, &PO, and R3As0. Reactions of CuX, (X = C1, Br, and I) with p y 0 and other heterocyclic amine N-oxides result in the formation of neutral dimeric complexes, [CuX,. P ~ O ] , In ~ .the reactions of Cu(C104), and Cu(BF4), with py0, however, ionic complexes, [Cu(pyO),](ClO,), and [Cu(pyO),](BF,), form4. Similarly, the reaction of Hg(C104)2 with p y o yields [Hg(pyO)6](C104),'. Reactions of R 3 P 0 and R 3 A s 0 with MX2 yield simple adducts, MX2.2R3E0 (M = C u , X = C 1 a n d B r , R = P h , E = P a n d A s 6 ; M = Z n , C d , a n d H g , X = C 1 , R = P h , E = P'). However, in the presence of noncoordinating ligands, C10, and R e 0 4 , ionic complexes, [ C U ( M ~ ~ E O ) ~ ( C ~ O ~ (E ) ] (=CP~ and O ~ )As)8, [Cu(Ph,EO),(ReO,)] (Re04)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
7 3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.4 From Neutral Oxygen Donor Ligands 3.7.2.4.1 By Ligand Displacement Reactions with Transition Metal Complexes
benzene at 70°C: (i-C3H7)2Hg + t-C4H90H(C3H7)zHg
+ C3H7HgOOC4H9
-
C3Hs
+ (i-C,H,)HgOO(t-C,Hg)
C3H7HgOC4H9
+ C3H7HgOC3H7
(a) (b)
The R,Cd compounds are more reactive than R2Hg, alkyls are more reactive than aryls, and ( R C 0 0 ) 2 are more reactive than ROOH. (M. T. POPE)
1. W. C. Schumb, C. N. Satterfield, R. L. Wentworth, Hydrogen Peroxide, Reinhold, New York, 1955. 2. N. V. Gorbunov, A. P. Purmal, Y. I. Skurlatov, Russ. J . Phys. Chem. (Engl. tranl.), 49,1169 (1975). 3. T. G. Brilkina, V. A. Shushunov, Reactions of Organometallic Compounds with Oxygen and Peroxides, Iliffe, London, 1969. 4. G. A. Razuvaev, V. A. Shushunov, V. A. Dodonov, T. G. Brilkina, Organic Peroxides, Vol. 3, D. Swern, ed., Wiley-Interscience, New York, 1972, p. 141. 3.7.2.3.2 By Oxidation of the Ligands Coordinated to the Metals
Phthalocyanines of Cu, Ag, Zn, and Hg are oxidized to the aquo or sulfato complexes, phthalimide, and ammonium ion by H 2 0 z in 17 M HzSO4l. (M. T. POPE)
1. B. D. Berezin, G. V. Sennikova, Kinet. Catal. (Engl. transl.), 9, 437 (1968).
3.7.2.4 From Neutral Oxygen Donor Ligands [Ethers, Aldehydes, Ketones, Pyridine N-Oxides, Phosphine Oxides, Arsine Oxides, and Dialkyl(ary1) Sulfoxides] 3.7.2.4.1 By Ligand Displacement Reactions with Transition Metal Complexes
(i) From Ethers. Although T H F reacts with ZnC1, and M[Hg(SCN),][M = Cu(I1) and Zn(II)] to yield the neutral adducts ZnCl,. 2THF and M[Hg(SCN),]. 2THF, respectively, it replaces the weak donor MeCN from [M(MeCN)6](SbC16), to form the sohates [CU(THF)6](SbCl& .2THF and [Zn(THF)6](SbC16)2,respectively'. (ii) From Ketones. Complexes of Cu(II), Ag(I), Au(III), Zn(II), Cd(II), and Hg(I1) with ketones are not known. However, spectroscopic studies in CH2C12 solution give evidence for the formation of [AgL,]BF4 (L = MeCOEt, Et,CO, MeCOPh, p-MeC6H4COMe, and p-C1C6H4COMe) and a solid complex [Ag(pMeC6H4COMe),]BF4 is isolated by cooling the CH2C12solution of the reactants2.
(iii) From py0, &PO, and R3As0. Reactions of CuX, (X = C1, Br, and I) with p y 0 and other heterocyclic amine N-oxides result in the formation of neutral dimeric complexes, [CuX,. P ~ O ] , In ~ .the reactions of Cu(C104), and Cu(BF4), with py0, however, ionic complexes, [Cu(pyO),](ClO,), and [Cu(pyO),](BF,), form4. Similarly, the reaction of Hg(C104)2 with p y o yields [Hg(pyO)6](C104),'. Reactions of R 3 P 0 and R 3 A s 0 with MX2 yield simple adducts, MX2.2R3E0 (M = C u , X = C 1 a n d B r , R = P h , E = P a n d A s 6 ; M = Z n , C d , a n d H g , X = C 1 , R = P h , E = P'). However, in the presence of noncoordinating ligands, C10, and R e 0 4 , ionic complexes, [ C U ( M ~ ~ E O ) ~ ( C ~ O ~ (E ) ] (=CP~ and O ~ )As)8, [Cu(Ph,EO),(ReO,)] (Re04)
8
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.4 From Neutral Oxygen Donor Ligands 3.7.2.4.2 By Insertion into the Metal-Ligand Bonds
(E = P and As)', [CU(HMPA)~](CIO~)~~, [Zn(HMPA)4](C104)2s,[Zn(Ph3PO)4](C104)z', CHg(Ph3PO)41(Clo4)zs,[Hgz(Ph3P0)61(C104)z9, and [Ag(HMpA)~l(C104)'form. (iv) From Me,SO. Reactions of Me2S0 with CdX, (X = C1 and Br) yield neutral complexes, CdX,. 2MezS0". However, with M(C104),, the solvates" [ C U ( M ~ ~ S O ) ~ ] ( and C~O [M(Me2SO)6] ~)~ (C104)2(M = Zn 1 1 , 1 2, Cd ,1 2 , 1 3 and ~ ~ 1 2 ~
form. (R. C. MEHROTRA, B. S. SARASWAT)
1. M. D. Heijer, Ph.D. thesis, Rijks University, Leiden, 1980. 2. D. R. Crist, Z. H. Hsieh, G. J. Jordan, F. P. Schinco, C. A. Maciorowski, J . A m . Chem. SOC.,96, 4932 (1974). 3. M. Kato, H. B. Jonassen, J. C. Fanning, Chem. Rev., 64,99 (1964); W. H. Watson, Inorg. Chem., 8, 1879 (1969). 4. D. S . Brown, J. D. Lee, B. G. A. Melsum, J . Chem. Soc., Chem. Commun., 852 (1968). 5. R. L. Carlin, R. Rottman, M. Dankleff, J. 0. Edwards, Inorg. Chem., 1, 182 (1962). 6. D. M. L. Goodgame, F. A. Cotton, J . Chem. Soc., 2298 (1961). 7. R. A. Jorge, C. Airoldi, A. P. Chagas, J . Chem. Soc., Dalton Trans., 1102 (1978). 8. N. M. Karayannis, C. M. Mikulski, L. L. Pytlewski, Inorg. Chim, Acta Rev., 5, 69 (1971). 9. D. L. Kepert, D. Taylor, A. H. White, J . Chem. SOC.,Dalton Trans., 1658 (1973). 10. W. L. Reynolds, Prog. Inorg. Chem., 12, l(1971). 11. F. A. Cotton, R. Francis, J . Am. Chem. SOC.,82, 2986 (1960). 12. M. Sandstrom, I. Persson, S . Ahrland, Acta Chem. Scand., A32, 607 (1978). 13. M. Sandstrom, Acta Chem. Scand., A32, 519 (1978). 14. M. Sandstrom, I. Persson, Acta Chem. Scand., A32, 95 (1978). 3.7.2.4.2 By Insertion into the Metal-Ligand Bonds
(i) From RCHO. Reaction of EtZnNPhz with RCHO in C6H6 results in the insertion of RCHO into the Zn-N bond':
EtZnNPh,
+ RCHO-
EtZnOCH(R)NPh,
(a)
(R = H, Me and n-Pr) Reactions of Me2Zn and MezCd (prepared in situ) with PhCH(R)CHOin EtzO similarly yield insertion products2: MezM + PhCH(R)CHO-
PhCH(R)CH(Me)OMMe
(b)
(M = Zn and Cd, R = Me, Et, and i-Pr) (ii) From R'R'CO. The reaction of PhzZn with PhzCO in refluxing c 6 H ~ M yields e
PhZnOCPh33: PhzZn + Ph,CO-
PhZnOCPh,
(4
However, reactions of RzZn (R = Et3 and i-Bu4; compounds having H attached to the fi-carbon atom) with R'R2C0 result in the elimination of alkene:
-
EtzZn + Ph,CO(Me,CHCH,),Zn
+ (Ph)(R)CO
EtZnOCHPh,
+ C2H4
(4
MezCHCHzZnOCH(R)Ph + Me2C=CH2 (e)
(R = Me, Et, i-Pr, t-Bu, and CF,)
1 4 )
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
8
3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.4 From Neutral Oxygen Donor Ligands 3.7.2.4.2 By Insertion into the Metal-Ligand Bonds
(E = P and As)', [CU(HMPA)~](CIO~)~~, [Zn(HMPA)4](C104)2s,[Zn(Ph3PO)4](C104)z', CHg(Ph3PO)41(Clo4)zs,[Hgz(Ph3P0)61(C104)z9, and [Ag(HMpA)~l(C104)'form. (iv) From Me,SO. Reactions of Me2S0 with CdX, (X = C1 and Br) yield neutral complexes, CdX,. 2MezS0". However, with M(C104),, the solvates" [ C U ( M ~ ~ S O ) ~ ] ( and C~O [M(Me2SO)6] ~)~ (C104)2(M = Zn 1 1 , 1 2, Cd ,1 2 , 1 3 and ~ ~ 1 2 ~
form. (R. C. MEHROTRA, B. S. SARASWAT)
1. M. D. Heijer, Ph.D. thesis, Rijks University, Leiden, 1980. 2. D. R. Crist, Z. H. Hsieh, G. J. Jordan, F. P. Schinco, C. A. Maciorowski, J . A m . Chem. SOC.,96, 4932 (1974). 3. M. Kato, H. B. Jonassen, J. C. Fanning, Chem. Rev., 64,99 (1964); W. H. Watson, Inorg. Chem., 8, 1879 (1969). 4. D. S . Brown, J. D. Lee, B. G. A. Melsum, J . Chem. Soc., Chem. Commun., 852 (1968). 5. R. L. Carlin, R. Rottman, M. Dankleff, J. 0. Edwards, Inorg. Chem., 1, 182 (1962). 6. D. M. L. Goodgame, F. A. Cotton, J . Chem. Soc., 2298 (1961). 7. R. A. Jorge, C. Airoldi, A. P. Chagas, J . Chem. Soc., Dalton Trans., 1102 (1978). 8. N. M. Karayannis, C. M. Mikulski, L. L. Pytlewski, Inorg. Chim, Acta Rev., 5, 69 (1971). 9. D. L. Kepert, D. Taylor, A. H. White, J . Chem. SOC.,Dalton Trans., 1658 (1973). 10. W. L. Reynolds, Prog. Inorg. Chem., 12, l(1971). 11. F. A. Cotton, R. Francis, J . Am. Chem. SOC.,82, 2986 (1960). 12. M. Sandstrom, I. Persson, S . Ahrland, Acta Chem. Scand., A32, 607 (1978). 13. M. Sandstrom, Acta Chem. Scand., A32, 519 (1978). 14. M. Sandstrom, I. Persson, Acta Chem. Scand., A32, 95 (1978). 3.7.2.4.2 By Insertion into the Metal-Ligand Bonds
(i) From RCHO. Reaction of EtZnNPhz with RCHO in C6H6 results in the insertion of RCHO into the Zn-N bond':
EtZnNPh,
+ RCHO-
EtZnOCH(R)NPh,
(a)
(R = H, Me and n-Pr) Reactions of Me2Zn and MezCd (prepared in situ) with PhCH(R)CHOin EtzO similarly yield insertion products2: MezM + PhCH(R)CHO-
PhCH(R)CH(Me)OMMe
(b)
(M = Zn and Cd, R = Me, Et, and i-Pr) (ii) From R'R'CO. The reaction of PhzZn with PhzCO in refluxing c 6 H ~ M yields e
PhZnOCPh33: PhzZn + Ph,CO-
PhZnOCPh,
(4
However, reactions of RzZn (R = Et3 and i-Bu4; compounds having H attached to the fi-carbon atom) with R'R2C0 result in the elimination of alkene:
-
EtzZn + Ph,CO(Me,CHCH,),Zn
+ (Ph)(R)CO
EtZnOCHPh,
+ C2H4
(4
MezCHCHzZnOCH(R)Ph + Me2C=CH2 (e)
(R = Me, Et, i-Pr, t-Bu, and CF,)
1 4 )
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.2Formation of the Oxygen-Group IB or llB Bond 3.7.2.5From Bidentate and Polydentate Oxygen Donor Ligands
9
Reactions of R2M (R = Me5 and n-Pr6, M = Zn and Cd; prepared in situ from MX2 and RMgX) with t-BuCH(CH2)2C(0)CH2CHz in EtzO yield mainly the insertion products: R2M
-
+ ~ - B u C H ( C H ~ ) ~ C ( O ) C H ~ CRHM~ O C ( R ) ( C H ~ ) ~ C H ( B U - ~ ) C H(f)~ C H ~ (R. C. MEHROTRA, B. S. SARASWAT)
1. 2. 3. 4. 5. 6.
J. Boersma, J. G. Noltes, J . Organornet. Chern., 21, P32 (1970). P. R. Jones, E. J. Goller, W. J. Kauffman, J . Org. Chem., 36, 3311 (1971). G. E. Coates, D. Ridley, J . Chem. SOC.,A , 1064 (1966). G. Giacomelli, L. Lardicci, R. Santi, J . Org. Chem., 39, 2736 (1974). P. R. Jones, E. J. Goller, W. J. Kauffman, J . Org. Chem., 34, 3566 (1969). P. R. Jones, W. J. Kauffman, E. J. Goller, J . Org. Chem., 36, 186 (1971).
3.7.2.5 From Bidentate and Polydentate Oxygen Donor Ligands (from Polyethers and Crown Ethers, Macrocycles, P,CPentanedione,etc.) (i) From Polyethers. Dimethoxyethane (dme) reacts with ZnBrzl, CdIZ2, and HgClZ3 to form 1 : 1 adducts, MX2.dme. However, CuC1, and ZnC12 react in the presence of SbC15 with excess dme to yield solvates4:
MC12
+ 2SbC15 + 3dme-
[M(drne),](SbCl6),
(a)
Reactions of higher homologues of dme with MXz yield neutral complexes, MXz. MeO(CH2CH20),Me (M = Cd, X = I; M = Hg, X = C1, n = 2-4) and 2MXz. MeO(CH,CH,O),Me (M = Cd, X = C1, and Br, n = 2-4),s3. In the presence of SbC15 in MeNO, solution, these polyethers react with MC12 to yield solvates4: {M[MeO(CHzCH20)2Me]z }(SbC16)2 (M
= Cu,
and Zn),
{M[ M ~ O ( C H Z C H Z ~ ) ~}(SbC16)2 M~]X (M = Cu, x
=
1.5; M
= Zn, x = 2),
{Zn[MeO(CH2CH20)4Me MeN02]}(SbC16)2and {M [MeO(CHzCHz0)5Mel}(SbC16)z (M = Cu, and Zn) (ii) From Crown Ethers. Reactions of n-BuOH solutions of CdClz and HgClz with dibenzo-18-crown-6 yield neutral complexes, [MClz. (dibenz0-18-crown-6)]~.Similarly, benzo-15-crown-5 and 18-crown-6 react with AgN03 and MX2 to form addition complexes, [AgN03 ~(benzo-l5-crown-5)-j6and [MX2.(18-crown-6)] (M = Zn, X = Br7; M = Cd2 and Hg8, X = C1, Br, and I), respectively. By contrast, CuX2 reacts with 1.5-crown-5 and 18-crown-6 to yield autocomplexes, [CuL][CuX4] (L = 15-crown-5, X = C14; L = 18-crown-6, X = C1 and Br’). The reaction of 18-crown-6 in MeNOZ solution with [Zn(MeNO&(SbC16)2 yields an ionic complex4: [Zn(MeN02)6](SbC16)2 + 18-crown-6-
[zn( 18-~rown-6)](SbC1~)~ + 6MeN02 (b)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.2Formation of the Oxygen-Group IB or llB Bond 3.7.2.5From Bidentate and Polydentate Oxygen Donor Ligands
9
Reactions of R2M (R = Me5 and n-Pr6, M = Zn and Cd; prepared in situ from MX2 and RMgX) with t-BuCH(CH2)2C(0)CH2CHz in EtzO yield mainly the insertion products: R2M
-
+ ~ - B u C H ( C H ~ ) ~ C ( O ) C H ~ CRHM~ O C ( R ) ( C H ~ ) ~ C H ( B U - ~ ) C H(f)~ C H ~ (R. C. MEHROTRA, B. S. SARASWAT)
1. 2. 3. 4. 5. 6.
J. Boersma, J. G. Noltes, J . Organornet. Chern., 21, P32 (1970). P. R. Jones, E. J. Goller, W. J. Kauffman, J . Org. Chem., 36, 3311 (1971). G. E. Coates, D. Ridley, J . Chem. SOC.,A , 1064 (1966). G. Giacomelli, L. Lardicci, R. Santi, J . Org. Chem., 39, 2736 (1974). P. R. Jones, E. J. Goller, W. J. Kauffman, J . Org. Chem., 34, 3566 (1969). P. R. Jones, W. J. Kauffman, E. J. Goller, J . Org. Chem., 36, 186 (1971).
3.7.2.5 From Bidentate and Polydentate Oxygen Donor Ligands (from Polyethers and Crown Ethers, Macrocycles, P,CPentanedione,etc.) (i) From Polyethers. Dimethoxyethane (dme) reacts with ZnBrzl, CdIZ2, and HgClZ3 to form 1 : 1 adducts, MX2.dme. However, CuC1, and ZnC12 react in the presence of SbC15 with excess dme to yield solvates4:
MC12
+ 2SbC15 + 3dme-
[M(drne),](SbCl6),
(a)
Reactions of higher homologues of dme with MXz yield neutral complexes, MXz. MeO(CH2CH20),Me (M = Cd, X = I; M = Hg, X = C1, n = 2-4) and 2MXz. MeO(CH,CH,O),Me (M = Cd, X = C1, and Br, n = 2-4),s3. In the presence of SbC15 in MeNO, solution, these polyethers react with MC12 to yield solvates4: {M[MeO(CHzCH20)2Me]z }(SbC16)2 (M
= Cu,
and Zn),
{M[ M ~ O ( C H Z C H Z ~ ) ~}(SbC16)2 M~]X (M = Cu, x
=
1.5; M
= Zn, x = 2),
{Zn[MeO(CH2CH20)4Me MeN02]}(SbC16)2and {M [MeO(CHzCHz0)5Mel}(SbC16)z (M = Cu, and Zn) (ii) From Crown Ethers. Reactions of n-BuOH solutions of CdClz and HgClz with dibenzo-18-crown-6 yield neutral complexes, [MClz. (dibenz0-18-crown-6)]~.Similarly, benzo-15-crown-5 and 18-crown-6 react with AgN03 and MX2 to form addition complexes, [AgN03 ~(benzo-l5-crown-5)-j6and [MX2.(18-crown-6)] (M = Zn, X = Br7; M = Cd2 and Hg8, X = C1, Br, and I), respectively. By contrast, CuX2 reacts with 1.5-crown-5 and 18-crown-6 to yield autocomplexes, [CuL][CuX4] (L = 15-crown-5, X = C14; L = 18-crown-6, X = C1 and Br’). The reaction of 18-crown-6 in MeNOZ solution with [Zn(MeNO&(SbC16)2 yields an ionic complex4: [Zn(MeN02)6](SbC16)2 + 18-crown-6-
[zn( 18-~rown-6)](SbC1~)~ + 6MeN02 (b)
10
3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.6 From Oxides of the Main Group Elements 3.7.2.6.1 By Reaction with the Metals
(iii) From Cryptands. Reaction of cryptand 222 with Ag03SCF3yields [Ag(cryptand 222)03SCF3'. Stability constants between metal ions and cryptand 222 show that the ligand is selective, particularly for H g Z + ,but also for Cd2+ and Znz+ ions".
(iv) From p-Dikctones. Addition of CuC1, or ZnC1, to a mixture of H(tfac) (tfac = trifluoroacetylacetonate) and N H 4 0 H yields M(tfac),l'. MC12
+ 2H(tfac) + 2NH40H-
M(tfac),
+ 2NH4C1 + 2 H z 0
(4
However, similar reaction with H(hfac) yields hydrated chelates, M(hfac)z. 2H20' '. Reaction of R,Zn (R = Et and Ph) with H(acac) is exothermic and results in the formation of RZn (acac)12: R2Zn
+ H(acac)-
C&
RZn(acac) + RH
(4
The liberated hydrocarbon can be removed under reduced pressure. In view of its simplicity and purity of the products, the reaction seems promising as a synthetic route to other P-diketonate complexes. (R. C. MEHROTRA, B. S. SARASWAT)
J. G. Noltes, J. W. G. van den Hurk, J . Organomet. Chem., I , 377 (1964). G. Wulfsberg, A. Weiss, J . Chem. Soc., Dalton Trans., 1640 (1977). R. Iwamoto, Bull. Chem. Soc. Jpn., 46, 1127 (1973). M. D. Heijer, Ph.D. thesis, Rijks University, Leiden, 1980. C. J. Pedersen, J . Am. Chem. Soc., 89, 2495, 7017 (1967). C. J. Pedersen, J . Am. Chem. Soc., 92, 386, (1970). A. Knochel, J. Klimes, J. Oehler, G. Rudolph, Inorg. Nucl. Chem. Lett., 11, 787 (1975). G. Wulfsberg, Inorg. Chem., 15, 1791 (1976). D. deVos, J. V. Daalen, A. C. Knegt, T. C. van Heyningen, L. P. Otto, M. W. Vonk, A. J. M. Wijsman, W. L. Driessen, J . Inorg. Nucl. Chem., 37, 1319 (1975). 10. J. M. Lehn, F. Montavon, Helu. Chim. Acta, 61, 67 (1978). 11. M. R. Kidd, R. S. Sager, W. H. Watson, Inorg. Chem., 6, 946 (1967). 12. J. Boersma, J. G. Noltes, J . Organomet. Chem., 1 3 , 291 (1968); J. Boersma, F. Verbeak, J. G. Noltes, J . Organomet. Chem., 33, C53 (1971). I. 2. 3. 4. 5. 6. 7. 8. 9.
3.7.2.6 From Oxides of the Main Group Elements 3.7.2.6.1 By Reaction with the Metals
Although in most cases formation of the metal oxide by reaction of the metal with a nonmetal oxide is thermodynamically feasible, such reactions are generally extremely slow. The metal can be considered inert'. The few examples of reported reactions involve NO,. Zinc and Cu react yielding ZnO and CuO; Ag and Hg yield the nitrates. Finely divided Zn reacts with C 0 2 above 300°C yielding ZnO and C. Red-hot Cu wire reacts with NO forming CuzO. Reaction of SOz with molten Cu yields CuzS and Cu,O, and with molten Ag, Ag2S04and Ag,S. The sulfate and sulfide are formed when Cd is heated in a stream of SOz. Liquid N2O4 dissolves metallic Ag, Zn, and Hg yielding the anhydrous nitrates and NO; Cu and Cd react in analogously with N z 0 4 dissolved in MeCOOEt, MeNOZ,or various nitriles'. With R4NC1, Cu, and Zn react with NzO4 giving [Cu(NO,),]- and [Zn(N03)4]2- anions. Nitrates of Cu, Zn, and Hg are also obtained from the metals and liquid N2OS3.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
10
3.7.2 Formation of the Oxygen-Group IB or llB Bond 3.7.2.6 From Oxides of the Main Group Elements 3.7.2.6.1 By Reaction with the Metals
(iii) From Cryptands. Reaction of cryptand 222 with Ag03SCF3yields [Ag(cryptand 222)03SCF3'. Stability constants between metal ions and cryptand 222 show that the ligand is selective, particularly for H g Z + ,but also for Cd2+ and Znz+ ions".
(iv) From p-Dikctones. Addition of CuC1, or ZnC1, to a mixture of H(tfac) (tfac = trifluoroacetylacetonate) and N H 4 0 H yields M(tfac),l'. MC12
+ 2H(tfac) + 2NH40H-
M(tfac),
+ 2NH4C1 + 2 H z 0
(4
However, similar reaction with H(hfac) yields hydrated chelates, M(hfac)z. 2H20' '. Reaction of R,Zn (R = Et and Ph) with H(acac) is exothermic and results in the formation of RZn (acac)12: R2Zn
+ H(acac)-
C&
RZn(acac) + RH
(4
The liberated hydrocarbon can be removed under reduced pressure. In view of its simplicity and purity of the products, the reaction seems promising as a synthetic route to other P-diketonate complexes. (R. C. MEHROTRA, B. S. SARASWAT)
J. G. Noltes, J. W. G. van den Hurk, J . Organomet. Chem., I , 377 (1964). G. Wulfsberg, A. Weiss, J . Chem. Soc., Dalton Trans., 1640 (1977). R. Iwamoto, Bull. Chem. Soc. Jpn., 46, 1127 (1973). M. D. Heijer, Ph.D. thesis, Rijks University, Leiden, 1980. C. J. Pedersen, J . Am. Chem. Soc., 89, 2495, 7017 (1967). C. J. Pedersen, J . Am. Chem. Soc., 92, 386, (1970). A. Knochel, J. Klimes, J. Oehler, G. Rudolph, Inorg. Nucl. Chem. Lett., 11, 787 (1975). G. Wulfsberg, Inorg. Chem., 15, 1791 (1976). D. deVos, J. V. Daalen, A. C. Knegt, T. C. van Heyningen, L. P. Otto, M. W. Vonk, A. J. M. Wijsman, W. L. Driessen, J . Inorg. Nucl. Chem., 37, 1319 (1975). 10. J. M. Lehn, F. Montavon, Helu. Chim. Acta, 61, 67 (1978). 11. M. R. Kidd, R. S. Sager, W. H. Watson, Inorg. Chem., 6, 946 (1967). 12. J. Boersma, J. G. Noltes, J . Organomet. Chem., 1 3 , 291 (1968); J. Boersma, F. Verbeak, J. G. Noltes, J . Organomet. Chem., 33, C53 (1971). I. 2. 3. 4. 5. 6. 7. 8. 9.
3.7.2.6 From Oxides of the Main Group Elements 3.7.2.6.1 By Reaction with the Metals
Although in most cases formation of the metal oxide by reaction of the metal with a nonmetal oxide is thermodynamically feasible, such reactions are generally extremely slow. The metal can be considered inert'. The few examples of reported reactions involve NO,. Zinc and Cu react yielding ZnO and CuO; Ag and Hg yield the nitrates. Finely divided Zn reacts with C 0 2 above 300°C yielding ZnO and C. Red-hot Cu wire reacts with NO forming CuzO. Reaction of SOz with molten Cu yields CuzS and Cu,O, and with molten Ag, Ag2S04and Ag,S. The sulfate and sulfide are formed when Cd is heated in a stream of SOz. Liquid N2O4 dissolves metallic Ag, Zn, and Hg yielding the anhydrous nitrates and NO; Cu and Cd react in analogously with N z 0 4 dissolved in MeCOOEt, MeNOZ,or various nitriles'. With R4NC1, Cu, and Zn react with NzO4 giving [Cu(NO,),]- and [Zn(N03)4]2- anions. Nitrates of Cu, Zn, and Hg are also obtained from the metals and liquid N2OS3.
3.7.2 Formation of the Oxyqen-Group IB or IIB Bond 3.7.2.7 From OH-, OR-, O2 , O2 3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
11
A mixture of liquid SO2 and MezSO dissolves Cu, Zn, and Cd yielding crystalline solvates of the disulfates of these metals4. (M. T. POPE)
1. Gmelins Handbuch der Anorganische Chemie, 8th ed., System Nr. 4 (Stickstoff); 9 (Schwefel) B1; 32 (Zink). 2. C. C. Addison, in Chemistry in Nonaqueous Ionizing Soloents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, Eds., Pergamon Press, New York, 1967, p. 1. 3. B. 0. Field, C. J. Hardy, Q. Ret. Chem. Soc., 18, 361 (1964). 4. W. D. Harrison, J. B. Gill, D. C. Goodall, J. Chem. Soc., Dalton Trans., 847 (1979). 3.7.2.6.2 By Reaction with Complexes of the Metals
Liquid N z 0 4 reacts with ZnClz to give the nitrate and NOCl. Liquid SOz reacts with Zn dialkyls yielding ZnO and the corresponding sulfoxide'. (M. T. POPE)
1. B. 0. Field, C. J. Hardy, Q. Ret.. Chem. Soc., 18, 361 (1964). 3.7.2.6.3 By Insertion into Metal-Ligand Bonds
Insertion reactions seems to be limited to those of COz',2.At 150°C, COz inserts into the Zn-C bond of a-bonded alkyls or aryls, Et2Zn
+ 2CO2-
(EtCOO)zZn
(a)
These reactions are catalyzed by organic N-bases such as bipyridine or N-methylimidazole'. Similar reactions with Cd and Hg do not occur, but some Cu complexes are quite reactive, e.g., (Ph3P),CuMe
+ COz
THF, -40°C
(Ph3P)2Cu(OOCMe)
(b) (M. T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Ado. Catal., 28, 79 (1979). 2. M. E. Volpin, I. S. Kolomnikov, in Urganometallic Reactions, Vol. 3, E. I. Becker, M. Tsutsui, Eds., 1975, p. 313.
3.7.2.7 From OH-, OR-,
Ol-,OF
3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
The solubility products of the hydroxides (or hydrous metal oxides) of Cu, Ag, Au, Zn, Cd, and Hg are listed in Table 1. Hydroxides are precipitated by treatment of complexes of the metals with OH-, provided the instability constants by the complexes' are of appropriate magnitude. [AuC14]--
OH-
AuzO3.xH20-
OH-
[Au(OH),]-
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.2 Formation of the Oxyqen-Group IB or IIB Bond 3.7.2.7 From OH-, OR-, O2 , O2 3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
11
A mixture of liquid SO2 and MezSO dissolves Cu, Zn, and Cd yielding crystalline solvates of the disulfates of these metals4. (M. T. POPE)
1. Gmelins Handbuch der Anorganische Chemie, 8th ed., System Nr. 4 (Stickstoff); 9 (Schwefel) B1; 32 (Zink). 2. C. C. Addison, in Chemistry in Nonaqueous Ionizing Soloents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, Eds., Pergamon Press, New York, 1967, p. 1. 3. B. 0. Field, C. J. Hardy, Q. Ret. Chem. Soc., 18, 361 (1964). 4. W. D. Harrison, J. B. Gill, D. C. Goodall, J. Chem. Soc., Dalton Trans., 847 (1979). 3.7.2.6.2 By Reaction with Complexes of the Metals
Liquid N z 0 4 reacts with ZnClz to give the nitrate and NOCl. Liquid SOz reacts with Zn dialkyls yielding ZnO and the corresponding sulfoxide'. (M. T. POPE)
1. B. 0. Field, C. J. Hardy, Q. Ret.. Chem. Soc., 18, 361 (1964). 3.7.2.6.3 By Insertion into Metal-Ligand Bonds
Insertion reactions seems to be limited to those of COz',2.At 150°C, COz inserts into the Zn-C bond of a-bonded alkyls or aryls, Et2Zn
+ 2CO2-
(EtCOO)zZn
(a)
These reactions are catalyzed by organic N-bases such as bipyridine or N-methylimidazole'. Similar reactions with Cd and Hg do not occur, but some Cu complexes are quite reactive, e.g., (Ph3P),CuMe
+ COz
THF, -40°C
(Ph3P)2Cu(OOCMe)
(b) (M. T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Ado. Catal., 28, 79 (1979). 2. M. E. Volpin, I. S. Kolomnikov, in Urganometallic Reactions, Vol. 3, E. I. Becker, M. Tsutsui, Eds., 1975, p. 313.
3.7.2.7 From OH-, OR-,
Ol-,OF
3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
The solubility products of the hydroxides (or hydrous metal oxides) of Cu, Ag, Au, Zn, Cd, and Hg are listed in Table 1. Hydroxides are precipitated by treatment of complexes of the metals with OH-, provided the instability constants by the complexes' are of appropriate magnitude. [AuC14]--
OH-
AuzO3.xH20-
OH-
[Au(OH),]-
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.2 Formation of the Oxyqen-Group IB or IIB Bond 3.7.2.7 From OH-, OR-, O2 , O2 3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
11
A mixture of liquid SO2 and MezSO dissolves Cu, Zn, and Cd yielding crystalline solvates of the disulfates of these metals4. (M. T. POPE)
1. Gmelins Handbuch der Anorganische Chemie, 8th ed., System Nr. 4 (Stickstoff); 9 (Schwefel) B1; 32 (Zink). 2. C. C. Addison, in Chemistry in Nonaqueous Ionizing Soloents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, Eds., Pergamon Press, New York, 1967, p. 1. 3. B. 0. Field, C. J. Hardy, Q. Ret. Chem. Soc., 18, 361 (1964). 4. W. D. Harrison, J. B. Gill, D. C. Goodall, J. Chem. Soc., Dalton Trans., 847 (1979). 3.7.2.6.2 By Reaction with Complexes of the Metals
Liquid N z 0 4 reacts with ZnClz to give the nitrate and NOCl. Liquid SOz reacts with Zn dialkyls yielding ZnO and the corresponding sulfoxide'. (M. T. POPE)
1. B. 0. Field, C. J. Hardy, Q. Ret.. Chem. Soc., 18, 361 (1964). 3.7.2.6.3 By Insertion into Metal-Ligand Bonds
Insertion reactions seems to be limited to those of COz',2.At 150°C, COz inserts into the Zn-C bond of a-bonded alkyls or aryls, Et2Zn
+ 2CO2-
(EtCOO)zZn
(a)
These reactions are catalyzed by organic N-bases such as bipyridine or N-methylimidazole'. Similar reactions with Cd and Hg do not occur, but some Cu complexes are quite reactive, e.g., (Ph3P),CuMe
+ COz
THF, -40°C
(Ph3P)2Cu(OOCMe)
(b) (M. T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Ado. Catal., 28, 79 (1979). 2. M. E. Volpin, I. S. Kolomnikov, in Urganometallic Reactions, Vol. 3, E. I. Becker, M. Tsutsui, Eds., 1975, p. 313.
3.7.2.7 From OH-, OR-,
Ol-,OF
3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
The solubility products of the hydroxides (or hydrous metal oxides) of Cu, Ag, Au, Zn, Cd, and Hg are listed in Table 1. Hydroxides are precipitated by treatment of complexes of the metals with OH-, provided the instability constants by the complexes' are of appropriate magnitude. [AuC14]--
OH-
AuzO3.xH20-
OH-
[Au(OH),]-
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.2 Formation of the Oxyqen-Group IB or IIB Bond 3.7.2.7 From OH-, OR-, O2 , O2 3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
11
A mixture of liquid SO2 and MezSO dissolves Cu, Zn, and Cd yielding crystalline solvates of the disulfates of these metals4. (M. T. POPE)
1. Gmelins Handbuch der Anorganische Chemie, 8th ed., System Nr. 4 (Stickstoff); 9 (Schwefel) B1; 32 (Zink). 2. C. C. Addison, in Chemistry in Nonaqueous Ionizing Soloents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, Eds., Pergamon Press, New York, 1967, p. 1. 3. B. 0. Field, C. J. Hardy, Q. Ret. Chem. Soc., 18, 361 (1964). 4. W. D. Harrison, J. B. Gill, D. C. Goodall, J. Chem. Soc., Dalton Trans., 847 (1979). 3.7.2.6.2 By Reaction with Complexes of the Metals
Liquid N z 0 4 reacts with ZnClz to give the nitrate and NOCl. Liquid SOz reacts with Zn dialkyls yielding ZnO and the corresponding sulfoxide'. (M. T. POPE)
1. B. 0. Field, C. J. Hardy, Q. Ret.. Chem. Soc., 18, 361 (1964). 3.7.2.6.3 By Insertion into Metal-Ligand Bonds
Insertion reactions seems to be limited to those of COz',2.At 150°C, COz inserts into the Zn-C bond of a-bonded alkyls or aryls, Et2Zn
+ 2CO2-
(EtCOO)zZn
(a)
These reactions are catalyzed by organic N-bases such as bipyridine or N-methylimidazole'. Similar reactions with Cd and Hg do not occur, but some Cu complexes are quite reactive, e.g., (Ph3P),CuMe
+ COz
THF, -40°C
(Ph3P)2Cu(OOCMe)
(b) (M. T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Ado. Catal., 28, 79 (1979). 2. M. E. Volpin, I. S. Kolomnikov, in Urganometallic Reactions, Vol. 3, E. I. Becker, M. Tsutsui, Eds., 1975, p. 313.
3.7.2.7 From OH-, OR-,
Ol-,OF
3.7.2.7.1 By Ligand Substitution Reactions with Complexes of the Metals
The solubility products of the hydroxides (or hydrous metal oxides) of Cu, Ag, Au, Zn, Cd, and Hg are listed in Table 1. Hydroxides are precipitated by treatment of complexes of the metals with OH-, provided the instability constants by the complexes' are of appropriate magnitude. [AuC14]--
OH-
AuzO3.xH20-
OH-
[Au(OH),]-
12
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.8 By Metal Atom and Related Reactions TABLE1.
SOLUBILITY PRODUCTS OF
c u+
METALHYDROXIDES AT 25°C”
14.7 - 19.32 - 1.71 - 20.6 - 15.52 to - 14.35 - 25.44 -
cuz Ag+ Ag3 Zn2+ CdZ+ Hg2+ +
+
-
16.61”
‘Dependent on the phase of Zn(OH), (s). Source: Ref. 1.
Ligand substitution by alkoxide seems not to have been widely investigated; two examples are:
+ LiOBu-t2ZnClz + 5NaOEt CuCl
-
+ LiCl NaZnz(OEt)5+ 2NaCl
THF
CuOBu-t
(b)’
(4
Substitution reactions with 0’-, 0 ; - ,and 0 ; have not been reported. (M. T. POPE) 1. R. M. Smith, A. E. Martell, Eds., Vol. 4, Critical Stability Constants, Plenum Press, New York,
1976. 2. T. Tsuda, T. Hashimoto, T. Tsaegusa, J. Am. Chem. Soc., 94, 658 (1972). 3.7.2.7.2 By Oxidation of the Metals and Their Complexes
Zinc metal dissolves rapidly in 30% NaOH yielding H z and [Zn(OH),(H,O)]-. Although Cd(0H)’ is soluble in concentrated NaOH, the metal is unreactive. Anodic oxidation of Hg, Ag, and Au in alkaline solutions leads to Hg(OH),, [Ag(OH),]-, and [Au(OH),]-. The yellow trivalent silver complex is slowly reduced by the solvent (tliz= 100min; 1.2M KOH, 27°C) to Ag1Ag1”02(“Ago”)’. Copper and Zn are converted to CuO and ZnO upon heating with N a 2 0 2 .Zinc is also converted to the oxide when heated with the oxides of Cd, Ni, Fe, Cu, Pb, Sn, W, Os, or Re. Copper(1) t-butoxide is oxidized to Cu(0Bu-t)’ by (t-Bu)’O2 in C6H6 solution’. (M. T. POPE)
1. L. J. Kirschenbaum, L. Mrozowski, Inorg. Chem., 17, 3718 (1978). 2. T. Tsuda, T. Hashimoto, T. Tsaegusa, J. Am. Chem. Soc., 94, 658 (1972).
3.7.2.8 By Metal Atom and Related Reactions
Codeposition of Ag atoms with 0’ under microscale matrix isolation conditions 12 K in inert gas) causes electron transfer. Two products are observed spectroscopically, Ag’O; and Ag’Oi’. When mixtures of Ag atoms and O z / C O are codeposited, (
N
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
12
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.8 By Metal Atom and Related Reactions TABLE1.
SOLUBILITY PRODUCTS OF
c u+
METALHYDROXIDES AT 25°C”
14.7 - 19.32 - 1.71 - 20.6 - 15.52 to - 14.35 - 25.44 -
cuz Ag+ Ag3 Zn2+ CdZ+ Hg2+ +
+
-
16.61”
‘Dependent on the phase of Zn(OH), (s). Source: Ref. 1.
Ligand substitution by alkoxide seems not to have been widely investigated; two examples are:
+ LiOBu-t2ZnClz + 5NaOEt CuCl
-
+ LiCl NaZnz(OEt)5+ 2NaCl
THF
CuOBu-t
(b)’
(4
Substitution reactions with 0’-, 0 ; - ,and 0 ; have not been reported. (M. T. POPE) 1. R. M. Smith, A. E. Martell, Eds., Vol. 4, Critical Stability Constants, Plenum Press, New York,
1976. 2. T. Tsuda, T. Hashimoto, T. Tsaegusa, J. Am. Chem. Soc., 94, 658 (1972). 3.7.2.7.2 By Oxidation of the Metals and Their Complexes
Zinc metal dissolves rapidly in 30% NaOH yielding H z and [Zn(OH),(H,O)]-. Although Cd(0H)’ is soluble in concentrated NaOH, the metal is unreactive. Anodic oxidation of Hg, Ag, and Au in alkaline solutions leads to Hg(OH),, [Ag(OH),]-, and [Au(OH),]-. The yellow trivalent silver complex is slowly reduced by the solvent (tliz= 100min; 1.2M KOH, 27°C) to Ag1Ag1”02(“Ago”)’. Copper and Zn are converted to CuO and ZnO upon heating with N a 2 0 2 .Zinc is also converted to the oxide when heated with the oxides of Cd, Ni, Fe, Cu, Pb, Sn, W, Os, or Re. Copper(1) t-butoxide is oxidized to Cu(0Bu-t)’ by (t-Bu)’O2 in C6H6 solution’. (M. T. POPE)
1. L. J. Kirschenbaum, L. Mrozowski, Inorg. Chem., 17, 3718 (1978). 2. T. Tsuda, T. Hashimoto, T. Tsaegusa, J. Am. Chem. Soc., 94, 658 (1972).
3.7.2.8 By Metal Atom and Related Reactions
Codeposition of Ag atoms with 0’ under microscale matrix isolation conditions 12 K in inert gas) causes electron transfer. Two products are observed spectroscopically, Ag’O; and Ag’Oi’. When mixtures of Ag atoms and O z / C O are codeposited, (
N
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
12
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.8 By Metal Atom and Related Reactions TABLE1.
SOLUBILITY PRODUCTS OF
c u+
METALHYDROXIDES AT 25°C”
14.7 - 19.32 - 1.71 - 20.6 - 15.52 to - 14.35 - 25.44 -
cuz Ag+ Ag3 Zn2+ CdZ+ Hg2+ +
+
-
16.61”
‘Dependent on the phase of Zn(OH), (s). Source: Ref. 1.
Ligand substitution by alkoxide seems not to have been widely investigated; two examples are:
+ LiOBu-t2ZnClz + 5NaOEt CuCl
-
+ LiCl NaZnz(OEt)5+ 2NaCl
THF
CuOBu-t
(b)’
(4
Substitution reactions with 0’-, 0 ; - ,and 0 ; have not been reported. (M. T. POPE) 1. R. M. Smith, A. E. Martell, Eds., Vol. 4, Critical Stability Constants, Plenum Press, New York,
1976. 2. T. Tsuda, T. Hashimoto, T. Tsaegusa, J. Am. Chem. Soc., 94, 658 (1972). 3.7.2.7.2 By Oxidation of the Metals and Their Complexes
Zinc metal dissolves rapidly in 30% NaOH yielding H z and [Zn(OH),(H,O)]-. Although Cd(0H)’ is soluble in concentrated NaOH, the metal is unreactive. Anodic oxidation of Hg, Ag, and Au in alkaline solutions leads to Hg(OH),, [Ag(OH),]-, and [Au(OH),]-. The yellow trivalent silver complex is slowly reduced by the solvent (tliz= 100min; 1.2M KOH, 27°C) to Ag1Ag1”02(“Ago”)’. Copper and Zn are converted to CuO and ZnO upon heating with N a 2 0 2 .Zinc is also converted to the oxide when heated with the oxides of Cd, Ni, Fe, Cu, Pb, Sn, W, Os, or Re. Copper(1) t-butoxide is oxidized to Cu(0Bu-t)’ by (t-Bu)’O2 in C6H6 solution’. (M. T. POPE)
1. L. J. Kirschenbaum, L. Mrozowski, Inorg. Chem., 17, 3718 (1978). 2. T. Tsuda, T. Hashimoto, T. Tsaegusa, J. Am. Chem. Soc., 94, 658 (1972).
3.7.2.8 By Metal Atom and Related Reactions
Codeposition of Ag atoms with 0’ under microscale matrix isolation conditions 12 K in inert gas) causes electron transfer. Two products are observed spectroscopically, Ag’O; and Ag’Oi’. When mixtures of Ag atoms and O z / C O are codeposited, (
N
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.2 Formation of the Oxygen-Group IB or IIB Bond 3.7.2.8 By Metal Atom and Related Reactions
13
CO complexes with the Agio; species2: Ag
+ CO +
0 2
12 K
7 OC-Ag' inert gas
0;
Observation of vc=o at 2165 cm-' in the IR spectrum indicates that CO is complexed to a cation site (free CO absorbs at 2140cm-'). Electron transfer does not occur when Cu and Au are codeposited with O 2 on a microscale. With Cu, C U ( O ~is) formed, ~~ but with Au the monocomplex Au(02) is formed4. Mixtures of O2 and CO with Au yield OC-Au-C03 and OC-Au-0 as intermediates3-', AU + CO AU
+
+ CO2
[
OC-AU
0 2
C-
[OC-Au-01
:7]
+ C02
(b)
(4
Codeposition of Cu, Ag, and Au at 77 K with 02/adamantane yields paramgnetic 1 : 1 M : O2 adducts that have been characterized by electron spin resonance spectros ~ o p y ' ~Most . of the unpaired spin density resides in a z* orbital on the two 0 atoms, with a low unpaired spin density on the metal atom. The Ag-02 and Au-O2 are side-on bonded, while the Cu-02 is end-on bonded. In rare gas matrices at 4 K, both M-O2 and M(02), were detected and formulated as charge-separated pairs such as M + ( 0 2 ) - ' '. Silver atoms codeposited on a microscale with C 0 2 yield a weakly interacting, side-on-bonded complexg:
,c=o
Ag,
I
0
Macroscale synthetic metal atom reactions yield Ag-etherate complexes at low temperatures ( - 196 to -20cC)'2: Ag +
03
I
A g - 0 3
(4
I
Upon warming, the etherate complexes decompose to metal slurries that can be used as media for depositing Ag clusters on catalyst supports". Slurries of Cu, Zn, and Cd in ether solvents (etherates of small metal particles) serve as highly active sources of these metal^'^.'^. (K. J. KLABUNDE) 1. D. McIntosh, G. A. Ozin, Inorg. Chem., 16, 59 (1977). 2. H. Huber, G. A. Ozin, Inorg. Chem., 16, (1977). 3. M. Moskovits, G . A. Ozin, in Cryochemistry, M. Moskovits, G. A. Ozin, eds., Wiley-Interscience, New York, 1976, p. 261. 4. D. McIntosh, G. A. Ozin, Inorg. Chem., 15, 2896 (1976).
14 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.1 From Sulfur 3.7.3.1.1 By Direct Reaction with Metals 5. J. H. Darling, M. B. Garton-Sprenger, J. S. Ogden, J . Chem. Soc., Faraday Trans., 2, 75 (1973). 6. D. McIntosh, G. A. Ozin, Inorg. Chem., 16, 51 (1977). 7. J. K. Burdett, M. Poliakoff, J. J. Turner, H. Dubost, Adz. Infrared Raman Spectrosc., 2, 1 (1976). 8. D. McIntosh, M. Moskovits, G. A. Ozin, Inorg. Chem., 15, 1669 (1976). 9. G. A. Ozin, H. Huber, D. McIntosh, Inorg. Chem., 17, 1472 (1978). 10. J. S. Howard, R. Sutcliffe, B. Mile, J . Phys. Chem., 88, 4351 (1984). 11. P. H. Kasai, P. M. Jones, J . Phys. Chem., 90, 4239 (1986). 12. K. J. Klabunde, D. Ralston, R. Zoellner, H. Hattori, Y. Tanaka, J . Catal., 55, 213 (1978). 13. T. 0. Murdock, K. J. Klabunde, J . Org. Chem., 41, 1076 (1976). 14. K. J. Klabunde, T. 0. Murdock, J . Org. Chem., 44, 3901 (1979).
3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.1 From Sulfur 3.7.3.1.1 By Direct Reaction with Metals
The group IB and IIB elements except Au react directly with S',' producing binary sulfides. Sulfides Cu2S (chalcocite), Ag2S (acanthite), ZnS (zinc blende), CdS (wurtzjte), and HgS (cinnabar) occur as minerals. These ores are primary sources of the elements3. Both blue-black CuzS4 and black AgzS5 are synthesized by heating the pure metal with S: 2M(s) + S-M,S(s)
(a)
The stoichiometry of the Cu binary sulfide ranges from Cu1.75Sto CuzS, depending on temperature of formation6. The group IIB elements react with S to form sulfides7: M(s)
+ S-MS(s)
(b)
Reaction with Zn can be violent after initial heating'. Black HgS forms upon grinding S together with Hg9. Subliming the elements together produces red HgS. The black form converts to the red form upon digestion with alkali sulfide^',^. Copper powder, formed by heating the oxalate CuC204, reacts with S in CS2, producing Cu2S. Reaction of this sulfide with S in CS2 at 100°C under the pressure developed, produces brownish black CUS'~,". It converts back to Cu2S upon heating. 5 x lo9 Pa Heating the CuS (covellite) and S in a 1 : 1.2 mole ratio to 500°C under (50kbar), yields the dark purplish red pyrite, CuS1.912.Disulfides ZnSz and CdS (pyrite-type structures) are prepared at high pressure^'^. In diamagnetic CuS the metal ions are associated with a mixture of catenated S i - and S 2 - . Its normal covalent Sz . Only binary Ag,S in several crystalline structure can be represented as CU$')CU~')(S~)~ modifications is currently known. Numerous ternary sulfides of Cu and Ag are known6.
-
-
(J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4.
F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th ed., Wiley, New York, 1980. N. V. Sidgwick, Chemical Elements and Their Compounds, Clarendon Press, Oxford, 1950. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1975. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1016.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
14 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.1 From Sulfur 3.7.3.1.1 By Direct Reaction with Metals 5. J. H. Darling, M. B. Garton-Sprenger, J. S. Ogden, J . Chem. Soc., Faraday Trans., 2, 75 (1973). 6. D. McIntosh, G. A. Ozin, Inorg. Chem., 16, 51 (1977). 7. J. K. Burdett, M. Poliakoff, J. J. Turner, H. Dubost, Adz. Infrared Raman Spectrosc., 2, 1 (1976). 8. D. McIntosh, M. Moskovits, G. A. Ozin, Inorg. Chem., 15, 1669 (1976). 9. G. A. Ozin, H. Huber, D. McIntosh, Inorg. Chem., 17, 1472 (1978). 10. J. S. Howard, R. Sutcliffe, B. Mile, J . Phys. Chem., 88, 4351 (1984). 11. P. H. Kasai, P. M. Jones, J . Phys. Chem., 90, 4239 (1986). 12. K. J. Klabunde, D. Ralston, R. Zoellner, H. Hattori, Y. Tanaka, J . Catal., 55, 213 (1978). 13. T. 0. Murdock, K. J. Klabunde, J . Org. Chem., 41, 1076 (1976). 14. K. J. Klabunde, T. 0. Murdock, J . Org. Chem., 44, 3901 (1979).
3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.1 From Sulfur 3.7.3.1.1 By Direct Reaction with Metals
The group IB and IIB elements except Au react directly with S',' producing binary sulfides. Sulfides Cu2S (chalcocite), Ag2S (acanthite), ZnS (zinc blende), CdS (wurtzjte), and HgS (cinnabar) occur as minerals. These ores are primary sources of the elements3. Both blue-black CuzS4 and black AgzS5 are synthesized by heating the pure metal with S: 2M(s) + S-M,S(s)
(a)
The stoichiometry of the Cu binary sulfide ranges from Cu1.75Sto CuzS, depending on temperature of formation6. The group IIB elements react with S to form sulfides7: M(s)
+ S-MS(s)
(b)
Reaction with Zn can be violent after initial heating'. Black HgS forms upon grinding S together with Hg9. Subliming the elements together produces red HgS. The black form converts to the red form upon digestion with alkali sulfide^',^. Copper powder, formed by heating the oxalate CuC204, reacts with S in CS2, producing Cu2S. Reaction of this sulfide with S in CS2 at 100°C under the pressure developed, produces brownish black CUS'~,". It converts back to Cu2S upon heating. 5 x lo9 Pa Heating the CuS (covellite) and S in a 1 : 1.2 mole ratio to 500°C under (50kbar), yields the dark purplish red pyrite, CuS1.912.Disulfides ZnSz and CdS (pyrite-type structures) are prepared at high pressure^'^. In diamagnetic CuS the metal ions are associated with a mixture of catenated S i - and S 2 - . Its normal covalent Sz . Only binary Ag,S in several crystalline structure can be represented as CU$')CU~')(S~)~ modifications is currently known. Numerous ternary sulfides of Cu and Ag are known6.
-
-
(J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4.
F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th ed., Wiley, New York, 1980. N. V. Sidgwick, Chemical Elements and Their Compounds, Clarendon Press, Oxford, 1950. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1975. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1016.
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols
15
5. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Academic Press, New York, 1965, p. 1039. 6. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 725. 7. W. M. Latimer, J. H. Hilderbrand, Reference Book oflnorganic Chemistry, 3rd ed., Macmillan, New York, 1951. 8. J. W. Mellor, Modern Inorganic Chemistry, Longmans, London, 1939, p. 33. 9. L. Newell, R. N. Maxson, M. H. Filson, Inorg. Synth., 1, 19 (1939). 10. Covellite can be ground to a blue powder. See Ref. 3. 11. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Academic Press, New York, 1965, p. 1018. 12. R. A. Munson, Inorg. Chem., 5 , 1296 (1966). 13. T. A. Bither, R. J. Bouchard, W. H. Cloud, P. C. Donohue, W. J. Siemons, Inorg. Chem., 7,2208 (1968). 3.7.3.1.2 By Reaction with Metal Complexes
Few reactions of group IB and IIB metal complexes with S have been studied in detail. The cluster anion Cu8 [S,CC(C(O)O-Bu-t),];upon reaction with sulfur produces' [Cu5L4S4], where L is the dithiolate ligand. Here, disulfide ligands are present:
The S-S portion of the four cluster ligands bond to a formally Cu3+ ion, while the other metal ions are Cu'. The Au3+ ion can replace the Cu3+ to form [AuCu4L4S4]-. Sulfur addition to other 1,l-dithiolate ligands occurs', although few complexes have been characterized. The S-addition ring expansion products with metal dithio complexes are well documented structurally': M(S,CR),
+ S-
M(S,CR)(S,CR),-
1
The S-rich Zn complexes of dithioaryl acids can be synthesized by reacting S with the S-poor species'. (J. P. FACKLER, K. G. FACKLER)
1. D. Coucouvanis, Prog. Inorg. Chem., 26, 302 (1979); D. Coucouvanis, S. Kanodia, D. Swenson, S.-J. Chan, T. Studemann, N. C. Baenziger, R. Pedelty, M. Chu., J . Am. Chem. Soc., 115, 11271, (1993). 2. J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. SOC.,94, 7323 (1972).
3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols Sulfides of the common group IB and IIB ions precipitate from aqueous solutions with H 2 S (Table 1). Aqueous sulfates can be used to synthesize CuS, ZnS, and CdS, while ammonical A g N 0 3 and HgClz in 1N HC1 give AgzS and HgS, respectively, on
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols
15
5. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Academic Press, New York, 1965, p. 1039. 6. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 725. 7. W. M. Latimer, J. H. Hilderbrand, Reference Book oflnorganic Chemistry, 3rd ed., Macmillan, New York, 1951. 8. J. W. Mellor, Modern Inorganic Chemistry, Longmans, London, 1939, p. 33. 9. L. Newell, R. N. Maxson, M. H. Filson, Inorg. Synth., 1, 19 (1939). 10. Covellite can be ground to a blue powder. See Ref. 3. 11. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Academic Press, New York, 1965, p. 1018. 12. R. A. Munson, Inorg. Chem., 5 , 1296 (1966). 13. T. A. Bither, R. J. Bouchard, W. H. Cloud, P. C. Donohue, W. J. Siemons, Inorg. Chem., 7,2208 (1968). 3.7.3.1.2 By Reaction with Metal Complexes
Few reactions of group IB and IIB metal complexes with S have been studied in detail. The cluster anion Cu8 [S,CC(C(O)O-Bu-t),];upon reaction with sulfur produces' [Cu5L4S4], where L is the dithiolate ligand. Here, disulfide ligands are present:
The S-S portion of the four cluster ligands bond to a formally Cu3+ ion, while the other metal ions are Cu'. The Au3+ ion can replace the Cu3+ to form [AuCu4L4S4]-. Sulfur addition to other 1,l-dithiolate ligands occurs', although few complexes have been characterized. The S-addition ring expansion products with metal dithio complexes are well documented structurally': M(S,CR),
+ S-
M(S,CR)(S,CR),-
1
The S-rich Zn complexes of dithioaryl acids can be synthesized by reacting S with the S-poor species'. (J. P. FACKLER, K. G. FACKLER)
1. D. Coucouvanis, Prog. Inorg. Chem., 26, 302 (1979); D. Coucouvanis, S. Kanodia, D. Swenson, S.-J. Chan, T. Studemann, N. C. Baenziger, R. Pedelty, M. Chu., J . Am. Chem. Soc., 115, 11271, (1993). 2. J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. SOC.,94, 7323 (1972).
3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols Sulfides of the common group IB and IIB ions precipitate from aqueous solutions with H 2 S (Table 1). Aqueous sulfates can be used to synthesize CuS, ZnS, and CdS, while ammonical A g N 0 3 and HgClz in 1N HC1 give AgzS and HgS, respectively, on
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols
15
5. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Academic Press, New York, 1965, p. 1039. 6. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 725. 7. W. M. Latimer, J. H. Hilderbrand, Reference Book oflnorganic Chemistry, 3rd ed., Macmillan, New York, 1951. 8. J. W. Mellor, Modern Inorganic Chemistry, Longmans, London, 1939, p. 33. 9. L. Newell, R. N. Maxson, M. H. Filson, Inorg. Synth., 1, 19 (1939). 10. Covellite can be ground to a blue powder. See Ref. 3. 11. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Academic Press, New York, 1965, p. 1018. 12. R. A. Munson, Inorg. Chem., 5 , 1296 (1966). 13. T. A. Bither, R. J. Bouchard, W. H. Cloud, P. C. Donohue, W. J. Siemons, Inorg. Chem., 7,2208 (1968). 3.7.3.1.2 By Reaction with Metal Complexes
Few reactions of group IB and IIB metal complexes with S have been studied in detail. The cluster anion Cu8 [S,CC(C(O)O-Bu-t),];upon reaction with sulfur produces' [Cu5L4S4], where L is the dithiolate ligand. Here, disulfide ligands are present:
The S-S portion of the four cluster ligands bond to a formally Cu3+ ion, while the other metal ions are Cu'. The Au3+ ion can replace the Cu3+ to form [AuCu4L4S4]-. Sulfur addition to other 1,l-dithiolate ligands occurs', although few complexes have been characterized. The S-addition ring expansion products with metal dithio complexes are well documented structurally': M(S,CR),
+ S-
M(S,CR)(S,CR),-
1
The S-rich Zn complexes of dithioaryl acids can be synthesized by reacting S with the S-poor species'. (J. P. FACKLER, K. G. FACKLER)
1. D. Coucouvanis, Prog. Inorg. Chem., 26, 302 (1979); D. Coucouvanis, S. Kanodia, D. Swenson, S.-J. Chan, T. Studemann, N. C. Baenziger, R. Pedelty, M. Chu., J . Am. Chem. Soc., 115, 11271, (1993). 2. J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. SOC.,94, 7323 (1972).
3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols Sulfides of the common group IB and IIB ions precipitate from aqueous solutions with H 2 S (Table 1). Aqueous sulfates can be used to synthesize CuS, ZnS, and CdS, while ammonical A g N 0 3 and HgClz in 1N HC1 give AgzS and HgS, respectively, on
16 3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols TABLE 1. SOLUBILITIES'.~ O F GROUP IB AND IIB
AU2S3
ZnS CdS
HgS
H20
Solubility (g/100mL H 2 0 , 18°C)
Sulfide CU,S CUS A& Au~S AuS
SULFIDES IN
5 x 10-5 3 x 10-5 10-15 Soluble; forms colloid with H2S Insoluble; dissolves in KCN (eq.) of alkali polysulfide Insoluble; dissolves in KCN (eq.) of alkali polysulfide 7x (freshly precipitated) 1.3 x 10-4 10-24
-
precipitation with H2S. The Au compounds Au2S, AuS, and Au2S3 are produced from HzS under other conditions'. Sulfides or sulfide-containing mixtures are expected when H2S reacts with complexes of group IB and IIB metals2. Although syntheses of several heavy metal crystalline polysulfides are known3, only a few (e.g., the crystalline ammonium polysulfides, NH4C~S431and NH4AuS3) are characterized. The complex [(Et)3PAu]2Sforms5 from (Et),PAuCI with Na2S, and the pentasulfides ZnS5 and CdS5 form from alkali pentasulfide solutions5. Additional [AuL] ', L = phosphine, can be added to the neutral [LAu12S complexes6 to form cations of type [S(AUL),,](-~'"),with n up to 5. Other black complex polysulfides of composition ca. K2Cu3SlO4,C U ~ SCuS3, ~ ~ , and Cu2S3*form with Cu; K2S and HgS form yellow to reddish orange K6HgS4 upon heating at 36G780"C9. Chelating, organic dithiolates such as xanthates", M(S2COR),, react with a suspension of KSPh in MeCN in the presence of large cations such as [(Ph),P]+ to form crystalline [(Ph)4P]2M(SPh)4salts": '(S2COR)~-"'+ 4KSPh-
MeCN
M'(SPh)t-4'
(a)
Tetrahedral complexes". l 2 are formed with Zn(I1) and Cd(I1).With Cu(1) a cluster of stoichiometry [(Ph)4P]2Cu4(SPh)6forms" whose anion contain^'^ a tetrahedron of Cu(1) atoms with bridging [SPhl- units. Other M2-SR clusters of Cu(1) are with [Cu5(p2-SPh),I2- and [Cu,(p-SBu-t),] being formed by reaction of C U ( N O ~ ) ~ with PhSH and amines in EtOH. The Ag analogue, [(Me),N],[Ag,(SPh),], forms ~imilarly'~. Interaction of Cu(I1) with D-penicillamine16 and L-cysteine and its derivatives produces mixed valence species in the presence of added halides. Gold compounds are of interest in medicine". Thus many Au(1) thiolates, including that of stoichiometry (AuSR), have been prepared'': H[AuC14]
+ 3RSH-
(AuSRH)
+ RSSR + 4HC1
(b)
Phosphines form complexes such as (Et),PAuSPh". Complexes of Au with thiols such as L-cysteine and sulfurized terpenes, called liquid gold, are probably clusters2'. Bridging thiols such as (Me)2Au(p-SR)2Au(Me)2 form2132z from (Me)3Au and HSR. Complexes of Cu(1) and Ag(1) with SCN- form in aqueous s o l ~ t i o n ~The ~,~~. K[Au(SCN),] can be prepared from AuSCN in MeOH. Organometallic derivativesz5
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 17 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.2 From Hydrogen Sulfide, Hydrogen Polysulfides, and Thiols
such as [(Et)2AuSCN]2 are known. Complex anions of [S203]’- form with Ag(1) and Au(I), the latter by reduction of H[AuCl,] or [Au(NH3),I3+ with [Sz03]z-26. Reaction of PhSH with Zn salts in deoxygenated solutions of noncoordinating amines produces” clusters, e.g., [Zn4(SPh)lo]2- and [Zn4(SPh)8C12]2-], in addition to [Zn(SPh),12-. In alcoholic solvents [Zn,(SPh),(ROH)], are produced, along with other solvated clustersz7. Structures of the reactive organometallic compounds [MeZnSCH(Me)z]8 and [(MeZnSC(Me),15 are k n o ~ n ’ ~ , ~ ~ . Penicillamine, cysteine, and glutathione react with Zn(II), Cd(II), and Hg(II), bonding to the metal ions via the -SH groupz9.Other thiols behave similarly3’. Clusters are generally produced31 with Zn(I1) and Cd(I1). Reaction of HgO with mercaptans, RSH, leads32explosively (mercurium captans) to Hg(SR) derivatives, which are low melting [mp Hg(SEt)z,76”C] and soluble in organic solvents33. (J. P. FACKLER, K. G. FACKLER) G. Brauer, Handbook of Preparative Inorgnic Chemistry, Academic Press, New York, 1965. Handbook ofchemistry and Physics, 58th ed., R. C. West, ed., CRC Press, Cleveland, OH, 1977. K. A. Hoffman, F. Hochtlen, Chem. Ber., 36, 3090 (1903); 37, 245 (1904). H. Blitz, P. Hems, Berichte, 40, 974 (1907). A. Schiff, Ann. Chem., 115, 68 (1860). H. Schmidbaur, Gold Bull., 23, 1 (1990); Interdisciplinary Sci. Rev., 17, 213, (1992). F. Bodroux, C. R. Hebd. Ser. Acad. Sci., 130, 1397 (1900). A. Rossing, Z . Anorg. Chem., 25, 407 (1900). H. Sommer, R. Hoppe, Z. Anorg. Chem., 443, 201 (1978). S. R. Rao, Xanthates and Related Compounds, Dekker, New York, 1971. D. Coucouvanis, C. N. Murphy, E. Simhan, P. Stremple, M. Draganjoe, Inorg. Synth., 21, 23 (1981). 12. D. G. Holah, D. Coucouvanis, J . Am. Chem. Soc., 98,6917 (1975); D. Coucouvanis, D. Swenson, N. C. Baenziger, D. G. Holah, A. Kostikes, A. Simopoulos, V. Petrouleas, J . Am. Chem. Soc., 98, 5721 (1976); D. Swenson, N. C. Baenziger, D. Coucouvanis,J. Am. Chem. SOC.,100,1932 (1978). 13. I. G. Dance, J. C. Calbrese, Inorg. Chim. Acta, 19, L41 (1976). 14. I. G. Dance, J . Chem. Soc., Chem. Commun., 103 (1976). 15. I. G. Dance, J . Chem. Soc., Chem. Commun., 68 (1976). 16. A. Gergely, I. Sovago, in Metal Ions in Biological Systems, H. Sigel, ed., Dekker, New York, 1979. 17. F. Shaw, Inorg. Prospect. Biol. Med., 2, 287 (1979); R. V. Parish, S. M. Cottril, Gold Bull., 20, 3 (1987);R. V. Parish, Interdisciplinary Sci. Rev., 17,221, (1992); Proceedings 3rd Int. Conf. Gold and Silver in Medicine, Met. Based Drugs., 1, Nos. 5,6 (1994). 18. A. Akerstrom, Ark. Kern., 14, 387 (1959); Chem. Abstr., 54, 19888 (1960). 19. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 63; J. M. Forward, D. Bohmann, J. P. Fackler, Jr., R. J. Staples, Inorg. Chem., 34, 6330 (1995); P. J. Sadler, Ads. Inorg. Chem., 36, 1 (1991). 20. F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th ed., Wiley-Interscience, New York, 1980, p. 977. 21. H. Gilman, L. A. Woods, J. Am. Chem. Soc., 70, 550 (1948). 22. R. J. Puddephatt, P. J. Thompson, J . Organomet. Chem., 117,395 (1976). See also Ref. 18, p. 131. 23. N. V. Sidgwick, Chemical Elements and Their Compounds,Clarendon Press, Oxford, 1950, p. 157. 24. F. A. Cotton, G. Wilkinson, Adcanced Inorganic Chemistry, 4th ed., Wiley-Interscience, New York, 1980, p. 968. 25. W. L. Gent, C. S. Gibson, J . Chem. Soc., 1835 (1949). 26. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 58. 27. I. G. Dance,J. Am. Chem. Soc., 102, 3445 (1980). 28. G. W. Adamson, H. M. M. Shearer, J . Chem. Soc., Chem. Commun., 897 (1969). 29. C. A. McAuliffe, S. G. Murray, Inorgan. Chim. Acta Rev. 6, 103 (1972). 30. H. B. Burgi, Helo. Chim. Acta, 57, 513 (1974); G. M. Bennett, J . Chem. Soc., 2139 (1922). 31. R. A. Haberkorn, L. Que, Jr., W. 0.Gillum, R. H. Holm, C. S. Lin, R. C. Lord, Inorg. Chem., 15, 2408 (1976); H. F. DeBrabander, L. C. Van Poucke, J . Coord. Chem., 3, 301 (1974). 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
18 3.7 Formation of the Group VIB-Group IB or IIB Metal Bond
3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.3 From Thiocarbonyls, Thioethers, Organic Polysulfides
32. P. Klason, Berchte, 20, 3410 (1887). 33. N. V. Sidgwick, Chemical Elements and Their Compounds,Clarendon Press, Oxford, 1950, p. 320.
3.7.3.3 From Thiocarbonyls, Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
Discovery of group IB and IIB S complexes of physiological relevance' has accelerated efforts to form well-characterized model compounds. Thiourea yields the cluster cation {CU~[SC(NH~)~],,}+ from [CU(H20)6]SiF6 in HzOZ.With other noncoordinating anions and various substitutions on the N atoms, aqueous solutions produce3 species such as C U ~ [ S C ( N H ~ ) ~ ] ~ (and B F ~[CU(SCNHCH~CH~NH)~]~(SO~). )~ Complexes between SCNHCHzCHzNH and Ag(1) exist4. Ligands such as SP(Me)35 and [SP(Ph)2]CH26coordinate readily with Cu(1). which ~ ) ~ ] "contains , an The polymeric species [ C U C ~ ( S ~ C O C ~ H ~ - ~ - M SzCu(I)Cl2Cu(I)S2 core structure, form7 from freshly prepared CuCl and the xanthogen N M ~from ~ ) ~the (BF~)~ in CS2. Complex C U ~ ( M ~ ~ N C H ~ C H ~ S S C H ~ C H ~forms disulfide' and contains a central CuSSCuSS ring. Formation of Cu(I1) in a tetrahedral CuS4 thioacetamide ligand geometry is reported from 6oCo gamma irradiation of the Cu(1) complexesg. In aqueous solutions, dialkyl sulfides reduce" many Au(II1) complexes, forming Au(1) sulfides:
+
[ A U C I ~ ] ' H ~ O 2Rs-
AuCl(R2S)
+ R2SO + 2H'-
3C1-
(a)
Gold(1) halides react directly with dialkyl sulfides' '. Complexes such as {Au[SC(NH,),]}+ and (Ph),PSAuCl form. Oxidation of AuCl(SR2)with C12 produces AUCI,(SR~)'~. Dinuclear Au(I1) yield complexes containing sulfur-rich thiourea coordination, e.g., [SSC(NPh)NHPh] -, have been ~haracterized'~. The group IIB metal ions Zn(I1) and Cd(I1) form halide complexes of type MX2L2, where X = halide and L = thioethers or thiocarbonyl l i g a n d ~ ' ~ ' ' ~With . L= SCNCH2CH2kH,complexes of type [CdL4]X2 form. Crystalline Hg(I1) complexes with HgClz by precipitation as HgC12L2,n = 1-4. An acetone L = SC(NH2)2form solution of MeHgN03 reacts'* with (Me),S yielding [MeHgS(Me)z]+. (J. P. FACKLER, K. G. FACKLER) 1. K. D. Karlin, J. Zeta, Inorg. Perspect. B i d . Med., 2, 127 (1979);A. J. Welch, S. K. Chapman, eds., The Chemistry of the Copper and Zinc Triads, Royal Society of Chemistry, Cambridge, 1993. 2. A. G. Cash, E. H. Griffith, W. A. Spofford, 111, E. L. Amma, J . Chem. SOC.,Chem. Commun.,256, (1973). 3. M. S. Weininger, G. W. Hunt, E. L. Amma, J . Chem. SOC.,Chem. Commun., 1140 (1972). 4. G. T. Morgan, F. H. Burstall, J . Chem. Soc., 143 (1928). 5. P. G. Eller, P. W. R. Corfield, J . Chem. Soc., Chem. Commun., 105 (1971). 6. E. W. Ainscough, H. A. Bergen, A. M. Brodie, H. L. Brown, J . Inorg. Nucl. Chem.,38,337 (1975). 7. H. W. Chen, J. P. Fackler, Jr., D. P. Schussler, L. D. Thompson, J. Am. Chem. Soc., 100, 2370 (1978). 8. T. Ottersen, L. G. Warner, K. Seff, J . Inorg. Nucl. Chem., 35, 876 (1973). 9. U. Sakaguchi, A. W. Addison, J. Am. Chem. Soc., 99, 5189 (1977). 10. D. deFilippo, F. Devillanova, C. Preti, Inorg. Chem. Acta, 5, 103 (1971). 11. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 60. 12. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 86. 13. D. D. Heinrich, J. P. Fackler, Jr., J. Am. Chem. Soc., 119, 1260 (1987). 14. N. V. Sidgwick, Chemical Elements and Their Compounds,Clarendon Press, Oxford, 1950, p. 284.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
18 3.7 Formation of the Group VIB-Group IB or IIB Metal Bond
3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.3 From Thiocarbonyls, Thioethers, Organic Polysulfides
32. P. Klason, Berchte, 20, 3410 (1887). 33. N. V. Sidgwick, Chemical Elements and Their Compounds,Clarendon Press, Oxford, 1950, p. 320.
3.7.3.3 From Thiocarbonyls, Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
Discovery of group IB and IIB S complexes of physiological relevance' has accelerated efforts to form well-characterized model compounds. Thiourea yields the cluster cation {CU~[SC(NH~)~],,}+ from [CU(H20)6]SiF6 in HzOZ.With other noncoordinating anions and various substitutions on the N atoms, aqueous solutions produce3 species such as C U ~ [ S C ( N H ~ ) ~ ] ~ (and B F ~[CU(SCNHCH~CH~NH)~]~(SO~). )~ Complexes between SCNHCHzCHzNH and Ag(1) exist4. Ligands such as SP(Me)35 and [SP(Ph)2]CH26coordinate readily with Cu(1). which ~ ) ~ ] "contains , an The polymeric species [ C U C ~ ( S ~ C O C ~ H ~ - ~ - M SzCu(I)Cl2Cu(I)S2 core structure, form7 from freshly prepared CuCl and the xanthogen N M ~from ~ ) ~the (BF~)~ in CS2. Complex C U ~ ( M ~ ~ N C H ~ C H ~ S S C H ~ C H ~forms disulfide' and contains a central CuSSCuSS ring. Formation of Cu(I1) in a tetrahedral CuS4 thioacetamide ligand geometry is reported from 6oCo gamma irradiation of the Cu(1) complexesg. In aqueous solutions, dialkyl sulfides reduce" many Au(II1) complexes, forming Au(1) sulfides:
+
[ A U C I ~ ] ' H ~ O 2Rs-
AuCl(R2S)
+ R2SO + 2H'-
3C1-
(a)
Gold(1) halides react directly with dialkyl sulfides' '. Complexes such as {Au[SC(NH,),]}+ and (Ph),PSAuCl form. Oxidation of AuCl(SR2)with C12 produces AUCI,(SR~)'~. Dinuclear Au(I1) yield complexes containing sulfur-rich thiourea coordination, e.g., [SSC(NPh)NHPh] -, have been ~haracterized'~. The group IIB metal ions Zn(I1) and Cd(I1) form halide complexes of type MX2L2, where X = halide and L = thioethers or thiocarbonyl l i g a n d ~ ' ~ ' ' ~With . L= SCNCH2CH2kH,complexes of type [CdL4]X2 form. Crystalline Hg(I1) complexes with HgClz by precipitation as HgC12L2,n = 1-4. An acetone L = SC(NH2)2form solution of MeHgN03 reacts'* with (Me),S yielding [MeHgS(Me)z]+. (J. P. FACKLER, K. G. FACKLER) 1. K. D. Karlin, J. Zeta, Inorg. Perspect. B i d . Med., 2, 127 (1979);A. J. Welch, S. K. Chapman, eds., The Chemistry of the Copper and Zinc Triads, Royal Society of Chemistry, Cambridge, 1993. 2. A. G. Cash, E. H. Griffith, W. A. Spofford, 111, E. L. Amma, J . Chem. SOC.,Chem. Commun.,256, (1973). 3. M. S. Weininger, G. W. Hunt, E. L. Amma, J . Chem. SOC.,Chem. Commun., 1140 (1972). 4. G. T. Morgan, F. H. Burstall, J . Chem. Soc., 143 (1928). 5. P. G. Eller, P. W. R. Corfield, J . Chem. Soc., Chem. Commun., 105 (1971). 6. E. W. Ainscough, H. A. Bergen, A. M. Brodie, H. L. Brown, J . Inorg. Nucl. Chem.,38,337 (1975). 7. H. W. Chen, J. P. Fackler, Jr., D. P. Schussler, L. D. Thompson, J. Am. Chem. Soc., 100, 2370 (1978). 8. T. Ottersen, L. G. Warner, K. Seff, J . Inorg. Nucl. Chem., 35, 876 (1973). 9. U. Sakaguchi, A. W. Addison, J. Am. Chem. Soc., 99, 5189 (1977). 10. D. deFilippo, F. Devillanova, C. Preti, Inorg. Chem. Acta, 5, 103 (1971). 11. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 60. 12. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 86. 13. D. D. Heinrich, J. P. Fackler, Jr., J. Am. Chem. Soc., 119, 1260 (1987). 14. N. V. Sidgwick, Chemical Elements and Their Compounds,Clarendon Press, Oxford, 1950, p. 284.
3.7.3 Formation of the Bond Between Sulfur and a Group 18 or llB Element 3.7.3.4 Organic Thio Acids and Other Thio Acids of Main Group Elements 3.7.3.4.1 By Oxidation of the Metals or Their Complexes
19
15. S. Baggio, R. F. Baggio, P. K. dePerazzo, Acta Crystallogr., Sect. B, 2Q 2166 (1974). 16. I. Auken, Inorg. Synth., 6, 27 (1960). 17. P. D. Brotherton, P. C. Healy, C. L. Raston, A. H. White, J. Chem. SOC.,Dalton Trans., 334 (1973). 18. P. G. Goggin, R. J. Goodfellow, S. R. Haddock, J. G. Eary, J. Chem. Soc., Dalton Trans., 647 (1972). 3.7.3.4 From Organic Thio Acids and Other Thio Acids of Main Group Elements 3.7.3.4.1 By Oxidation of the Metals or Their Complexes
Products of anionic nucleophile reactions with CS2 are coordinating ligands (Table 1)'. Dithiophosphate and related ligands also bind metal ions readily through the S atoms. Xanthic acids and other 1,l-dithio acids are oxidized to disulfides by mild oxidizing agents: 2NuCS2H-
NuC(S)S-SC(S)Nu
+ 2 H f + 2e-
(a)
[Nu = -[OR], -[NR2], -[Ph], etc. (anionic nucleophiles)] These disulfides react2-' with activated forms of group IB and IIB metals to form 1,1-dithiolates:
3n NuC(S)Sz + M = M(SzCNu)2
(b)
The group IB compounds produced are clusters, e.g., [ C U S Z C N ( C ~ H ~Group ) ~ ] ~ ~IIB . ions Zn(1) and Cd(I1) produce M(S2CNu)2 derivatives, which can be polymeric if steric factors permit. Both Hg(1) and Hg(I1) species are known2. Oxidation of Cu(I), Ag(I), Au(III), and Hg(1) species can be accomplished with thiuramdisulfides, ( R ~ N S C Z )dixanthogens, ~, (ROCS2)2, and related disulfides. This reaction is generally important in syntheses of Cu(II), Ag(II), and Au(II1) dithiocarbamates:
TABLE1. MAJOR TYPESOF ~,~-DITHIOLATE AND DITHIOPHOSPHATE LICANDS
Ligand
Name
Formation"
Dithiocarboxylate Xanthate Thioxanthate Dithiocarbamate Dithiophosphinate" Dithiophosphates Trithiocarbonate 1,l-Ethylenedithiolate Dithiocarbimate
MgRz t CS2 ROH + CS, + base RSH t CS, +base RzNH + CS, t base R,PCl + Na,S ROH + P2S5 +base NazS + CS, RICH2 + CS, + base RNHz + CS, + base
"Arsenic derivatives also known
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.7.3 Formation of the Bond Between Sulfur and a Group 18 or llB Element 3.7.3.4 Organic Thio Acids and Other Thio Acids of Main Group Elements 3.7.3.4.1 By Oxidation of the Metals or Their Complexes
19
15. S. Baggio, R. F. Baggio, P. K. dePerazzo, Acta Crystallogr., Sect. B, 2Q 2166 (1974). 16. I. Auken, Inorg. Synth., 6, 27 (1960). 17. P. D. Brotherton, P. C. Healy, C. L. Raston, A. H. White, J. Chem. SOC.,Dalton Trans., 334 (1973). 18. P. G. Goggin, R. J. Goodfellow, S. R. Haddock, J. G. Eary, J. Chem. Soc., Dalton Trans., 647 (1972). 3.7.3.4 From Organic Thio Acids and Other Thio Acids of Main Group Elements 3.7.3.4.1 By Oxidation of the Metals or Their Complexes
Products of anionic nucleophile reactions with CS2 are coordinating ligands (Table 1)'. Dithiophosphate and related ligands also bind metal ions readily through the S atoms. Xanthic acids and other 1,l-dithio acids are oxidized to disulfides by mild oxidizing agents: 2NuCS2H-
NuC(S)S-SC(S)Nu
+ 2 H f + 2e-
(a)
[Nu = -[OR], -[NR2], -[Ph], etc. (anionic nucleophiles)] These disulfides react2-' with activated forms of group IB and IIB metals to form 1,1-dithiolates:
3n NuC(S)Sz + M = M(SzCNu)2
(b)
The group IB compounds produced are clusters, e.g., [ C U S Z C N ( C ~ H ~Group ) ~ ] ~ ~IIB . ions Zn(1) and Cd(I1) produce M(S2CNu)2 derivatives, which can be polymeric if steric factors permit. Both Hg(1) and Hg(I1) species are known2. Oxidation of Cu(I), Ag(I), Au(III), and Hg(1) species can be accomplished with thiuramdisulfides, ( R ~ N S C Z )dixanthogens, ~, (ROCS2)2, and related disulfides. This reaction is generally important in syntheses of Cu(II), Ag(II), and Au(II1) dithiocarbamates:
TABLE1. MAJOR TYPESOF ~,~-DITHIOLATE AND DITHIOPHOSPHATE LICANDS
Ligand
Name
Formation"
Dithiocarboxylate Xanthate Thioxanthate Dithiocarbamate Dithiophosphinate" Dithiophosphates Trithiocarbonate 1,l-Ethylenedithiolate Dithiocarbimate
MgRz t CS2 ROH + CS, + base RSH t CS, +base RzNH + CS, t base R,PCl + Na,S ROH + P2S5 +base NazS + CS, RICH2 + CS, + base RNHz + CS, + base
"Arsenic derivatives also known
20 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.4 Organic Thio Acids and Other Thio Acids of Main Group Elements 3.7.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals
With gold, oxidation to Au(II1) species such as A u ( S ~ C N Rand ~ ) ~[Au(S2CNRZ),]Br occurs8. Oxidation of C U ( S ~ C N Rwith ~ ) ~C12 and Brz produces a square-planar Cu(II1) species of known structureg: Br2
-
+ C U ( S ~ C N R ~ ) ~BrzCu(SzCNRz)+ 0.5(R2NCS2)2
(4
Structures of the square-planar CuS, cations of type [Cu(S2CNR2),] are known3. Thiuramdisulfides are used for analysis of Cu, Ag, Hg, and Zn”. Reaction of the Zn(II), Cd(II),and Hg(I1)dithiocarbamates with halogens produces thiuramdisulfide complexes with the oxidation state of the metal unchanged3. Reaction of S on polysulfides with Zn(S2CAr)2,where Ar =C6H5and its derivatives, leads to Zn(S3CAr)21i.Other oxidants also can be used to produce these S-rich complexes. +-
(J. P. FACKLER, K. G. FACKLER) 1. S. R. Rao, Xanthates and Related Compounds, Dekker, New York, 1971. 2. D. Coucouvanis, Prog. Inorg. Chem., 11, 234 (1970); 26, 301 (1979). Excellent, authoratative reviews on metal 1,l-dithiolate chemistry. 3. J. Willemse, J. A. Cras, J. J. Steggerda, C. P. Keijzers, Struct. Bonding, 28, 83 (1976). 4. J. R. Wasson, G. M. Woltermann, H. J. Stoklosa, Fortschr, Chem. Forsch, 35, 65, (1973). 5. R. P. Burns, F. P. McCullough, C. A. McAuliffe, Adu. Inorg. Chem. Radiochem, 23, 211 (1980). 6. J. P. Fackler, Jr., Adv. Chem. Series, 150, 394 (1976). 7. J. P. Fackler, Jr., Prog. Inorg. Chem., 21, 55 (1976). 8. P. R. Beurskiens, J. A. Cras, J. G. M. Van der Linden, Inorg. Chem., 9, 475 (1970). 9. P. T. Beurskens, J. A. Cras, J. J. Steggerda, Inorg. Chem., 7 , 810 (1968). 10. G. D. Thorn, R. A. Ludwig, The Dithiocarbamates and Related Compounds, Elsevier, New York, 1962. 11. J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. Sot., 94, 7323 (1972). 3.7.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals and
by Sulfur Atom Abstraction
Group IA or IIA metal salts of 1,l-dithio acids form readily from CSz and organic bases (see 3.7.3.4.1, Table 1). These salts in alcohols, ethers, acetonitrile, or similar polar organic solvents react with metal salts in the same solvent producing dithiolate‘: MX,
-
+ nM’S2CY
M(S2CY), + nM’X
(a)
For example, NaPh reacts with CS2 in T H F or MeCN. MBr2 (M = Zn or Cu) and (Et),NCl are added to form [(Et)4M]2M(S2CC5H4)22. Amines, alcohols, and thiols can be used with CS2 without isolating the group IA metal salt. A basic salt or hydroxide of the group IB or IIB metal is sufficient. Organomagnesium halide reagents yield Zn(S2CR)z.An alternative method3 involves formation of the S-rich Zn dithioacid derivatives by reaction of aldehydes with ammonium polysulfides. The Zn(S3CR), species react readily4 with phosphines or KCN, forming Zn(S2CR),. The importance of various Zn(S2CNR2)2species as rubber vulcanization catalysts5 and the Cu(1) and Zn(I1) dialkyldithiophosphates as oil antioxidant additives6 prompts their study. They can be used in metathesis to form other metal derivatives:
+
n-Zn(S2CNu)2 2MX,-2M(S2CNu)2
+ nZnX2
(b)
(J. P. FACKLER, K. G. FACKLER) 1. R. P. Burns, F. P. McCullough, C. A. McAuliffe, Adv. Inorg. Chem. Radiochem, 23, 211 (1980). 2. P. C. Saving, R. D. Bereman, Inorg. Chem., 12, 173 (1973).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
20 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.4 Organic Thio Acids and Other Thio Acids of Main Group Elements 3.7.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals
With gold, oxidation to Au(II1) species such as A u ( S ~ C N Rand ~ ) ~[Au(S2CNRZ),]Br occurs8. Oxidation of C U ( S ~ C N Rwith ~ ) ~C12 and Brz produces a square-planar Cu(II1) species of known structureg: Br2
-
+ C U ( S ~ C N R ~ ) ~BrzCu(SzCNRz)+ 0.5(R2NCS2)2
(4
Structures of the square-planar CuS, cations of type [Cu(S2CNR2),] are known3. Thiuramdisulfides are used for analysis of Cu, Ag, Hg, and Zn”. Reaction of the Zn(II), Cd(II),and Hg(I1)dithiocarbamates with halogens produces thiuramdisulfide complexes with the oxidation state of the metal unchanged3. Reaction of S on polysulfides with Zn(S2CAr)2,where Ar =C6H5and its derivatives, leads to Zn(S3CAr)21i.Other oxidants also can be used to produce these S-rich complexes. +-
(J. P. FACKLER, K. G. FACKLER) 1. S. R. Rao, Xanthates and Related Compounds, Dekker, New York, 1971. 2. D. Coucouvanis, Prog. Inorg. Chem., 11, 234 (1970); 26, 301 (1979). Excellent, authoratative reviews on metal 1,l-dithiolate chemistry. 3. J. Willemse, J. A. Cras, J. J. Steggerda, C. P. Keijzers, Struct. Bonding, 28, 83 (1976). 4. J. R. Wasson, G. M. Woltermann, H. J. Stoklosa, Fortschr, Chem. Forsch, 35, 65, (1973). 5. R. P. Burns, F. P. McCullough, C. A. McAuliffe, Adu. Inorg. Chem. Radiochem, 23, 211 (1980). 6. J. P. Fackler, Jr., Adv. Chem. Series, 150, 394 (1976). 7. J. P. Fackler, Jr., Prog. Inorg. Chem., 21, 55 (1976). 8. P. R. Beurskiens, J. A. Cras, J. G. M. Van der Linden, Inorg. Chem., 9, 475 (1970). 9. P. T. Beurskens, J. A. Cras, J. J. Steggerda, Inorg. Chem., 7 , 810 (1968). 10. G. D. Thorn, R. A. Ludwig, The Dithiocarbamates and Related Compounds, Elsevier, New York, 1962. 11. J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. Sot., 94, 7323 (1972). 3.7.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals and
by Sulfur Atom Abstraction
Group IA or IIA metal salts of 1,l-dithio acids form readily from CSz and organic bases (see 3.7.3.4.1, Table 1). These salts in alcohols, ethers, acetonitrile, or similar polar organic solvents react with metal salts in the same solvent producing dithiolate‘: MX,
-
+ nM’S2CY
M(S2CY), + nM’X
(a)
For example, NaPh reacts with CS2 in T H F or MeCN. MBr2 (M = Zn or Cu) and (Et),NCl are added to form [(Et)4M]2M(S2CC5H4)22. Amines, alcohols, and thiols can be used with CS2 without isolating the group IA metal salt. A basic salt or hydroxide of the group IB or IIB metal is sufficient. Organomagnesium halide reagents yield Zn(S2CR)z.An alternative method3 involves formation of the S-rich Zn dithioacid derivatives by reaction of aldehydes with ammonium polysulfides. The Zn(S3CR), species react readily4 with phosphines or KCN, forming Zn(S2CR),. The importance of various Zn(S2CNR2)2species as rubber vulcanization catalysts5 and the Cu(1) and Zn(I1) dialkyldithiophosphates as oil antioxidant additives6 prompts their study. They can be used in metathesis to form other metal derivatives:
+
n-Zn(S2CNu)2 2MX,-2M(S2CNu)2
+ nZnX2
(b)
(J. P. FACKLER, K. G. FACKLER) 1. R. P. Burns, F. P. McCullough, C. A. McAuliffe, Adv. Inorg. Chem. Radiochem, 23, 211 (1980). 2. P. C. Saving, R. D. Bereman, Inorg. Chem., 12, 173 (1973).
3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 21 3.7.3.5 From Bidentate and Polydentate Sulfur Donor Atoms 3.7.3.5.1 By Sulfur Addition, Oxidation and Sulfur Abstraction Reactions 3. 4. 5. 6.
J. P. Fackler, Jr., D. Coucouvanis, J. A. Fetchin, W. C. Seidel, J . Am. Chem. Soc., 90,2784 (1968). D. Coucouvanis, Prog. Inorg. Chem., 11, 234 (1970); 26, 301 (1979). W. Hoffman, Vulcanization and Vulcanizing Agents, MacLaren and Sons, London, 1967. T. Colcolough, Ind. Eng. Chem. Res., 26, 1888 (1987).
3.7.3.5 From Bidentate and Polydentate Sulfur Donor Atoms 3.7.3.5.1 By Sulfur Addition, Oxidation and Sulfur Abstraction Reactions
Routes to bidentate 1,2-dithiolene derivatives and both mono- and dithio-Pdiketones are varied. Toluene-3,4-dithiol and its derivatives are used for Zn, Cd, and Hg analysis'. Development of understanding of the chemistry of the related o-aminothiophenols, which stabilize Ni(IV)', stimulated much work in the 1960s. The 1,l-dithio anion, [S2CCN]-, formed from NaCN and CS2 in DMF, readily ) ~ ] ~ - These , solutions react extrudes S forming the l,2-dithio ion, [ C ~ S - S ~ C ~ ( C N MNT. with salts of Zn(II), Cd(II), Cu(II), and Au(III), producing the [M(MNT),]'- products. The complex charge varies with the metal, the ligand, and the conditions of preparation. Species with z = 0 and 2 are known3 for Zn and Cd, z = 0,1, and 2 for Cu, and z = 1 and 2 for gold. There are few reports of Ag(I)4 or Au(I)' complexes. Synthesis of M(S2C2R2),complexes of M=Cu, Au is achieved' from metal sulfides and alkynes. This is the preferred route6 with dithietes, (CF3)2C2S2.Polymeric [HgS2C2(CF3)2]nforms by reduction of the dithiete with Hg(1) compounds3. The acyloin reaction6 followed by acidification or further direct reaction with metal salts is preferred when R is electron donating: ArC(O)C(OH)HAr
+ P4S10
-
(Ar)2C2S2P(S)SHand other products
(a)
With dithietes, CuI(PPh3) and AuCl(PPh3) form [M(S2C2(CF3)2]- anions, which precipitate from C6H6 and are crystallized as salts using large cations'. Electron delocalization in these complexes is extensive. Reaction of P-diketones with H2S and I2 in EtOH saturated with HCl produces dithiolium salts8: RCOCH2COR
+
2H2S + 212
C,H,OH HCl
n
[RCSCHCSRI'I;
+ 2H20 + HI
(b)
Reduction of the dithiolium species with NaBH, gives the anionic dithio-P-diketonate7, which reacts with salts forming the metal derivative. Activated low-valent metal species ~ SacSac = also can be usedg to form the S complex. The Z n ( S a ~ S a c )complex, MeCSCHCSMe, is prepared by NaBH4 reduction of the dithiolium [ZnCl4I2- salt. Reaction of H2S with the P-diketone at OcC (in EtOH HCl) containing the appropriate metal ions produces the dithio-B-diketone derivative or (with Zn) its precursor dithiolium salt. With ethylacetoacetate as the P-diketone, trimeric [Cu(OEt-SacSac)13 forms'. Z n ( 0 E t - S a ~ S a cis) ~monomeric, and has a tetrahedral ZnS4 geometry. Various P-mercaptoketones react with Cu2 salts, producing yellow Cu(1) complexes' +
'3'
(J. P. FACKLER, K. G. FACKLER)
1. R. P. Burns, C. A. McAuliffe, Adu. Inorg. Radiochem., 22, 303 (1979). 2. W. Hieber, R. Bruck, Z. Anorg. Allgem. Chem., 269, 13 (1952).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 21 3.7.3.5 From Bidentate and Polydentate Sulfur Donor Atoms 3.7.3.5.1 By Sulfur Addition, Oxidation and Sulfur Abstraction Reactions 3. 4. 5. 6.
J. P. Fackler, Jr., D. Coucouvanis, J. A. Fetchin, W. C. Seidel, J . Am. Chem. Soc., 90,2784 (1968). D. Coucouvanis, Prog. Inorg. Chem., 11, 234 (1970); 26, 301 (1979). W. Hoffman, Vulcanization and Vulcanizing Agents, MacLaren and Sons, London, 1967. T. Colcolough, Ind. Eng. Chem. Res., 26, 1888 (1987).
3.7.3.5 From Bidentate and Polydentate Sulfur Donor Atoms 3.7.3.5.1 By Sulfur Addition, Oxidation and Sulfur Abstraction Reactions
Routes to bidentate 1,2-dithiolene derivatives and both mono- and dithio-Pdiketones are varied. Toluene-3,4-dithiol and its derivatives are used for Zn, Cd, and Hg analysis'. Development of understanding of the chemistry of the related o-aminothiophenols, which stabilize Ni(IV)', stimulated much work in the 1960s. The 1,l-dithio anion, [S2CCN]-, formed from NaCN and CS2 in DMF, readily ) ~ ] ~ - These , solutions react extrudes S forming the l,2-dithio ion, [ C ~ S - S ~ C ~ ( C N MNT. with salts of Zn(II), Cd(II), Cu(II), and Au(III), producing the [M(MNT),]'- products. The complex charge varies with the metal, the ligand, and the conditions of preparation. Species with z = 0 and 2 are known3 for Zn and Cd, z = 0,1, and 2 for Cu, and z = 1 and 2 for gold. There are few reports of Ag(I)4 or Au(I)' complexes. Synthesis of M(S2C2R2),complexes of M=Cu, Au is achieved' from metal sulfides and alkynes. This is the preferred route6 with dithietes, (CF3)2C2S2.Polymeric [HgS2C2(CF3)2]nforms by reduction of the dithiete with Hg(1) compounds3. The acyloin reaction6 followed by acidification or further direct reaction with metal salts is preferred when R is electron donating: ArC(O)C(OH)HAr
+ P4S10
-
(Ar)2C2S2P(S)SHand other products
(a)
With dithietes, CuI(PPh3) and AuCl(PPh3) form [M(S2C2(CF3)2]- anions, which precipitate from C6H6 and are crystallized as salts using large cations'. Electron delocalization in these complexes is extensive. Reaction of P-diketones with H2S and I2 in EtOH saturated with HCl produces dithiolium salts8: RCOCH2COR
+
2H2S + 212
C,H,OH HCl
n
[RCSCHCSRI'I;
+ 2H20 + HI
(b)
Reduction of the dithiolium species with NaBH, gives the anionic dithio-P-diketonate7, which reacts with salts forming the metal derivative. Activated low-valent metal species ~ SacSac = also can be usedg to form the S complex. The Z n ( S a ~ S a c )complex, MeCSCHCSMe, is prepared by NaBH4 reduction of the dithiolium [ZnCl4I2- salt. Reaction of H2S with the P-diketone at OcC (in EtOH HCl) containing the appropriate metal ions produces the dithio-B-diketone derivative or (with Zn) its precursor dithiolium salt. With ethylacetoacetate as the P-diketone, trimeric [Cu(OEt-SacSac)13 forms'. Z n ( 0 E t - S a ~ S a cis) ~monomeric, and has a tetrahedral ZnS4 geometry. Various P-mercaptoketones react with Cu2 salts, producing yellow Cu(1) complexes' +
'3'
(J. P. FACKLER, K. G. FACKLER)
1. R. P. Burns, C. A. McAuliffe, Adu. Inorg. Radiochem., 22, 303 (1979). 2. W. Hieber, R. Bruck, Z. Anorg. Allgem. Chem., 269, 13 (1952).
22 3.7 Formation of the Group VIB-Group IB or IIB Metal Bond
3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.6 From Sulfur Containing Anions (S' ~, S?-, [HS - 1, [RS] - )
3. J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). 4. R. Heber, E. Hoyer, J . Prakt. Chem., 318,19 (1976); D. D. Heinrich,J. P. Fackler, Jr., Inorg. Chim. Acta, 116, 159 (1986). 5. R. M. Davila, A. Elduque, R. J. Staples, M. Harless, J. P. Fackler, Jr., Inorg. Chim. Actu, 21 7,45 (1994); R. M. Davila, R. J. Staples, J. P. Fackler, Jr., Orgunometallics, 13, 418 (1994). 6. G. N. Schrauzer, Trans. M e t . Chem., 4, 299 (1968). 7. A. Davidson, D. V. Howe, E. T. Shawl, Inorg. Chem., 6, 458 (1967). 8. T. N. Lockyer, R. L. Martin, Prog. Inorg. Chem., 6, 458 (1967). 9. J. P. Fackler, Jr., A. F. Masters, unpublished observations, 1979. 10. H. Tanaka, A. Yokoyama, Chem. Pharm. Bull. (Tokyo),8, 275, 280, 1008, 1012 (1960). 11. S. E. Livingstone, Q. Rev. Chem. Soc., 19, 386 (1965). 3.7.3.5.2 By Ligand Substitution Reactions
Substitution reactions yield dithiolates','. The Cu, Ag, Au, and Zn derivatives, (M[S2C2(CN)J2}'-, are prepared starting with NazSzC2(CN)2and appropriate metal salts3. With AuBr2(S2CNBu2)as the starting compound, a mixed ligand complex forms4:
A mixed ligand complex of Cu is also known5. Formation of Au(II), Cd(II), and Hg(I1) complexes with various a-dithiols has been investigated6. Numerous aminothiol complexes form, such as the Cu(I), Zn(I1) and Cd(I1) derivatives of a-thioamidopyridine, C5H4NCSNHz.Derivatives of Ag(I), Zn(I1) and Hg(I1) are known with H02CCH(SH)CH2C02H6.Cysteine, HSCH2CH(NH2)COOH, forms compounds with the group IB and IIB e l e r n e n t ~ ' ~Many ~ . Au(1) studies with thiols have attempted to model the role of gold in medicine-crys~therapy~. (J. P. FACKLER, K. G. FACKLER) 1. J. A. McCleverty,Prog. Inorg. Chem., 10,49 (1968);J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 2. E. I. Stiefel, R. Eisenberg, R. C. Rosenberg, H. B. Gray, J . Am. Chem. Soc., 88, 2956 (1966). 3. A. Davidson, R. H. Holm, Inorg. Synth., 10, 8 (1967). 4. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 89. 5 . J. G. M. Van der Linden, H. G. J. Van der Roer, Inorg. Chim. Acta, 5, 524 (1971). 6. S. E. Livingstone, Q. Rev. Chem. Soc., 19, 386 (1965). 7. C. A. McAuliffe, S. G. Murray, Inorg. Chim. Acta Reo., 6, 55 (1972). 8. K. K. Karlin, J. Zubieta, Inorg. Perspect. B i d . Med., 2, 127 (1979). 9. R. V. Parish, Interdisciplinary Sci. Rev. 17, 221 (1992); R. J. Puddephatt, Comp. Coord. Chem., 5, 861 (1987).
3.7.3.6 From Sulfur Containing Anions (S2-, S:-,
[HS-1, [RSI-)
The group IB and IIB elements exhibit a high affinity for anionic sulfur ligands. Treatment of the divalent salts with Sz - ion precipitates the binary sulfides, MS (M = Cu, H g black; M = Zn, white; M = Cd, yellow). Copper(I1) sulfide, like the mineral covellite, is more descriptively formulated as Cut's. Cu:Sz'. Whereas black M2S solids are precipitated from Cu', Ag', and AU' solutions, Hgi' yields a mixture of black HgS
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
22 3.7 Formation of the Group VIB-Group IB or IIB Metal Bond
3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.6 From Sulfur Containing Anions (S' ~, S?-, [HS - 1, [RS] - )
3. J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). 4. R. Heber, E. Hoyer, J . Prakt. Chem., 318,19 (1976); D. D. Heinrich,J. P. Fackler, Jr., Inorg. Chim. Acta, 116, 159 (1986). 5. R. M. Davila, A. Elduque, R. J. Staples, M. Harless, J. P. Fackler, Jr., Inorg. Chim. Actu, 21 7,45 (1994); R. M. Davila, R. J. Staples, J. P. Fackler, Jr., Orgunometallics, 13, 418 (1994). 6. G. N. Schrauzer, Trans. M e t . Chem., 4, 299 (1968). 7. A. Davidson, D. V. Howe, E. T. Shawl, Inorg. Chem., 6, 458 (1967). 8. T. N. Lockyer, R. L. Martin, Prog. Inorg. Chem., 6, 458 (1967). 9. J. P. Fackler, Jr., A. F. Masters, unpublished observations, 1979. 10. H. Tanaka, A. Yokoyama, Chem. Pharm. Bull. (Tokyo),8, 275, 280, 1008, 1012 (1960). 11. S. E. Livingstone, Q. Rev. Chem. Soc., 19, 386 (1965). 3.7.3.5.2 By Ligand Substitution Reactions
Substitution reactions yield dithiolates','. The Cu, Ag, Au, and Zn derivatives, (M[S2C2(CN)J2}'-, are prepared starting with NazSzC2(CN)2and appropriate metal salts3. With AuBr2(S2CNBu2)as the starting compound, a mixed ligand complex forms4:
A mixed ligand complex of Cu is also known5. Formation of Au(II), Cd(II), and Hg(I1) complexes with various a-dithiols has been investigated6. Numerous aminothiol complexes form, such as the Cu(I), Zn(I1) and Cd(I1) derivatives of a-thioamidopyridine, C5H4NCSNHz.Derivatives of Ag(I), Zn(I1) and Hg(I1) are known with H02CCH(SH)CH2C02H6.Cysteine, HSCH2CH(NH2)COOH, forms compounds with the group IB and IIB e l e r n e n t ~ ' ~Many ~ . Au(1) studies with thiols have attempted to model the role of gold in medicine-crys~therapy~. (J. P. FACKLER, K. G. FACKLER) 1. J. A. McCleverty,Prog. Inorg. Chem., 10,49 (1968);J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 2. E. I. Stiefel, R. Eisenberg, R. C. Rosenberg, H. B. Gray, J . Am. Chem. Soc., 88, 2956 (1966). 3. A. Davidson, R. H. Holm, Inorg. Synth., 10, 8 (1967). 4. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 89. 5 . J. G. M. Van der Linden, H. G. J. Van der Roer, Inorg. Chim. Acta, 5, 524 (1971). 6. S. E. Livingstone, Q. Rev. Chem. Soc., 19, 386 (1965). 7. C. A. McAuliffe, S. G. Murray, Inorg. Chim. Acta Reo., 6, 55 (1972). 8. K. K. Karlin, J. Zubieta, Inorg. Perspect. B i d . Med., 2, 127 (1979). 9. R. V. Parish, Interdisciplinary Sci. Rev. 17, 221 (1992); R. J. Puddephatt, Comp. Coord. Chem., 5, 861 (1987).
3.7.3.6 From Sulfur Containing Anions (S2-, S:-,
[HS-1, [RSI-)
The group IB and IIB elements exhibit a high affinity for anionic sulfur ligands. Treatment of the divalent salts with Sz - ion precipitates the binary sulfides, MS (M = Cu, H g black; M = Zn, white; M = Cd, yellow). Copper(I1) sulfide, like the mineral covellite, is more descriptively formulated as Cut's. Cu:Sz'. Whereas black M2S solids are precipitated from Cu', Ag', and AU' solutions, Hgi' yields a mixture of black HgS
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
22 3.7 Formation of the Group VIB-Group IB or IIB Metal Bond
3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.6 From Sulfur Containing Anions (S' ~, S?-, [HS - 1, [RS] - )
3. J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). 4. R. Heber, E. Hoyer, J . Prakt. Chem., 318,19 (1976); D. D. Heinrich,J. P. Fackler, Jr., Inorg. Chim. Acta, 116, 159 (1986). 5. R. M. Davila, A. Elduque, R. J. Staples, M. Harless, J. P. Fackler, Jr., Inorg. Chim. Actu, 21 7,45 (1994); R. M. Davila, R. J. Staples, J. P. Fackler, Jr., Orgunometallics, 13, 418 (1994). 6. G. N. Schrauzer, Trans. M e t . Chem., 4, 299 (1968). 7. A. Davidson, D. V. Howe, E. T. Shawl, Inorg. Chem., 6, 458 (1967). 8. T. N. Lockyer, R. L. Martin, Prog. Inorg. Chem., 6, 458 (1967). 9. J. P. Fackler, Jr., A. F. Masters, unpublished observations, 1979. 10. H. Tanaka, A. Yokoyama, Chem. Pharm. Bull. (Tokyo),8, 275, 280, 1008, 1012 (1960). 11. S. E. Livingstone, Q. Rev. Chem. Soc., 19, 386 (1965). 3.7.3.5.2 By Ligand Substitution Reactions
Substitution reactions yield dithiolates','. The Cu, Ag, Au, and Zn derivatives, (M[S2C2(CN)J2}'-, are prepared starting with NazSzC2(CN)2and appropriate metal salts3. With AuBr2(S2CNBu2)as the starting compound, a mixed ligand complex forms4:
A mixed ligand complex of Cu is also known5. Formation of Au(II), Cd(II), and Hg(I1) complexes with various a-dithiols has been investigated6. Numerous aminothiol complexes form, such as the Cu(I), Zn(I1) and Cd(I1) derivatives of a-thioamidopyridine, C5H4NCSNHz.Derivatives of Ag(I), Zn(I1) and Hg(I1) are known with H02CCH(SH)CH2C02H6.Cysteine, HSCH2CH(NH2)COOH, forms compounds with the group IB and IIB e l e r n e n t ~ ' ~Many ~ . Au(1) studies with thiols have attempted to model the role of gold in medicine-crys~therapy~. (J. P. FACKLER, K. G. FACKLER) 1. J. A. McCleverty,Prog. Inorg. Chem., 10,49 (1968);J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 2. E. I. Stiefel, R. Eisenberg, R. C. Rosenberg, H. B. Gray, J . Am. Chem. Soc., 88, 2956 (1966). 3. A. Davidson, R. H. Holm, Inorg. Synth., 10, 8 (1967). 4. R. J. Puddephatt, The Chemistry of Gold, Elsevier, New York, 1978, p. 89. 5 . J. G. M. Van der Linden, H. G. J. Van der Roer, Inorg. Chim. Acta, 5, 524 (1971). 6. S. E. Livingstone, Q. Rev. Chem. Soc., 19, 386 (1965). 7. C. A. McAuliffe, S. G. Murray, Inorg. Chim. Acta Reo., 6, 55 (1972). 8. K. K. Karlin, J. Zubieta, Inorg. Perspect. B i d . Med., 2, 127 (1979). 9. R. V. Parish, Interdisciplinary Sci. Rev. 17, 221 (1992); R. J. Puddephatt, Comp. Coord. Chem., 5, 861 (1987).
3.7.3.6 From Sulfur Containing Anions (S2-, S:-,
[HS-1, [RSI-)
The group IB and IIB elements exhibit a high affinity for anionic sulfur ligands. Treatment of the divalent salts with Sz - ion precipitates the binary sulfides, MS (M = Cu, H g black; M = Zn, white; M = Cd, yellow). Copper(I1) sulfide, like the mineral covellite, is more descriptively formulated as Cut's. Cu:Sz'. Whereas black M2S solids are precipitated from Cu', Ag', and AU' solutions, Hgi' yields a mixture of black HgS
23 3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or IIB Element 3.7.3.6 From Sulfur Containing Anions (S2- , S : - , [HS - 1, [RS] - )
and elemental Hg. Black HgS is thermally unstable and decomposes in the presence of polysulfides or Hg2Clz to the red cinnabar HgS'-3. Although AuzS is polymeric, a soluble derivative, Au,S(PMe3)', is formed from reaction of AuCl(PMe,) and H2S4. Polysulfides often result from reaction of S8 with a base. [NH4I2Sx,where most often x = 4,5, forms when HzS is bubbled through a suspension of S8 in NH3(aq).This generates the blue radical S;' Treatment of Cu(I1) salts with polysulfide solutions (made from NH3, H2S, and s8) yields the complexes [Cu,(S,),]". Covellite (CuS) was prepared by the reaction of Cu, S8, and refluxing pyridine. The same reaction performed at room temperature yields CuS and C U ~ ( S ~ ) ~ Supercritical ( ~ ~ ) ~ ~ 'NH3 . (170°C)as solvent is used to make the M(I) salt [ C U ( S ~ ) , ] ~ -Alkali ' ~ . metal salts of C u S i form by heating Cu and M2S417'18.With sulfur atoms at the corners of a cube and the Cu atoms along the edges, [ C U ~ ~ S , ]can ~ - be prepared by heating a Cu(I1) salt with EtS- and adding Li2S to the cooled resultant s o l ~ t i o n ' Addition ~. of S8 instead of LizS results in more stable tetra- and pentasulfido complexes, e.g., [ C U ~ ( S ~ ) ~ ( -S ~ ' O ). ]A' low temperature (90OC) synthesis of the Chevrel phase Cu(NH3)Mo3S9involves reacting CuC1, with ( N H & M o S ~ ~ ' .
'.
sYS,S
I
s-s I \ s, /s
\s
s-cu /
SCA)
s-s 2 1 Polysulfide solutions as in 1 and 2 are used with Ag(1) compounds such as [AgSg]-, [Ag2(S6)z]2-2 2 , and [Ag2S20]4-2 3 and supercritical NH3 to form [Ag(S4),I3- 1 6 . The three-dimensional [Ag,S,] -, [Ag,S4]-, and [Ag6S4]'- were made by reaction of a base, s8, and the metal in a supercritical amine24325. Reacting Au2(S02),with electrolytically formed short chain S produces AuzS, as compared to its reaction with HzS, which yields A u ~ SAu2S3 ~ ~ ~is prepared . by reacting HAuC14 with H2SZ7.Linear gold(1)can be seen in [Au2S8]'-, made when ethanolic polysulfide is contacted with HAuC14", and in [AuS,]- made from reaction of [Au(SCN),]- with S:- '*. Analogous polysulfides of Zn and Cd typically are not synthesized like the Cu, Ag, and Au anions. Instead, they can form from reactions of the [M(SR),12- and their reactions with s8, as in Scheme 1". [zn(SR)4l2--
Br-(S),-Bz
[zn(sR)2(s4)lZ-
Br-(S),-Bz
_
Ph,P
_
_
f
[zn(sR)z(s5)12
I
[zn(S4)2I2
Scheme 1 However, N-methylimidazole appears to work well in solubilizing Zn with S8 to form ZnS6(N-MeIm)230.The [Hg(S6),l2- ion is obtained by reaction of H ~ ( O A Cwith )~
24 3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.6 From Sulfur Containing Anions (S' - , S f - , [HS- 1, [RS] - )
~
aqueous polysulfide, unlike the [cd(S6),l2- ion counterpart, which is not observed31. Compounds of the type ZnS6(N-donor)2are easily prepared by heating the elements and the N-donor solvent. Subsequent reaction of ZnS,(TMEDA) with Ph4PS6 yields (Ph4P)2[ZnS12]32.Myriad metal sulfide cations were created upon laser ablation of the transition metal and subsequent reaction with gaseous S833. Organic thiolates coordinate with these elements. Because of its moderated basicity, pentafluorothiophenolate exhibits simpler coordination chemistry than its hydrocarbon analogues. Salts of Zn, Cd, and Hg react with NaSC6F5 giving tetracoordinated complexes, [M(sc6F5)4]2-, which are isolable as their crystalline [Et,N]' salts. For the group IB elements, [Et4N] salts of the corresponding two-coordinated complexes [M(SC6F5)2]-, are isolated34. Chemistry of Cu(1) thiolates involves polymeric [Cu(SR)]. (R = CH3, t-Bu, Ph), [Cu(SPh),I2-, [Cu2(SCH3),]-, [Cu4(SPh),12-, and [ C U ~ ( S ~ - B -U3)5~, 3]6 . These polymers can be kept in solution if R contains an auxiliary ionic function such as-NMe: or -SO; 3 7 . The adamantyl ( P ~ , P ) [ C U ~ I ~ ~ ( S Rand ) , , ] (Ph4P)2 ~~ [ C U I ~ ( S R ) , ]were ~~ made by reacting Cu' with In(SR)i. A 16-membered c u & twisted ring with alternating Cu and S atoms was made by refluxing CuCl and 2,4,6-'Pr3C6H2SHwith Et3N4'. Phosphine Cu(1) thiolates can be prepared from CuCl(PR3)with NaSR or by dissolution of [Cu(SR)], in basic phosphine solutions41. Even richer chemistry for the Ag thiolates exists; crystalline salts of [Ag5(SPh)7]2-, [Ag6(SPh)s12-, and [Ag12(SPh)16]4- are obtained from the reaction of PhSH, Bu3N, and AgN0342-44. +
Ph
I0
IS\AP
R
RS/(y%wS
9 S-
s s--u--SR
R
RR
?I;/
PhS
o=cu
Ace* AcO
[\;7Tg{!sph
S-Au-PEt
S
Ph [CU(SC~H~P~S)I~ "4g5(SPh)71ZAuranofin 3 4 5 A bulky ligand creates molecular species; e.g., addition of (R3Si)2R'CSH with Et3N and AgN0, yields [AgSC(SiR3)3], (n = 3, R = Me and Ph, R' = SiMe2Ph; n = 4, R = Me, R' = SiMe3; n = 8, R = Me, R = H)45.Coordination of mercaptides to Au(1) appears to give predominantly polymeric complexes, which are marketed as antiarthritic agents, e.g., Ad-thiomalate (Myochrysine) and Ad-thioglucose (Auranofin). Solganol, another Ad-thioglucose, has ability to inhibit HIV4,. A 1 : 1 reaction of AuCl(PMe3) and NaSMe yields Au(SMe)(PMe3),while a 2: 1 ratio forms [MeS{Au(PMe,)},]+. An excess of AuCl(PMe3) yields the tetrahedrally coordinated thiolate, [MeS{Au(PMe,)),l2+ 47. Polymeric Cu(1) mercaptides can reliably be prepared as:
+ + RSM-
C U ~ O 2RSHCuCl
Cu2+
+ 2RSH-
2Cu(SR) + H2O
Cu(SR) + MCl
2Cu(SR)
+ 0.5R2S2 + 2Hf
(a)48 (b)49 (c)41
25 3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.6 From Sulfur Containing Anions (S‘-, S:-, [HS - 1, [RS] - ) Heteronuclear coinage metal thiolates are prepared by initial reactions of CuC1, (or CuCl in CH3CN) or AgN03 in MeOH with -SCH2CH2S- (L) to form [Cu4L3I2- or [AggL6I3-. These react with [Et4N][AuBr2] to form [Au2Cu4L4I2-,[Au3Cu3L4]’-, or [ A u ~ A ~ ~ 5L0 . ~ ] ~ Copper(I1) thiolates are unstable with respect to autoreduction, although several Cu(I1) thiolates containing polyamine ligands form in s o l ~ t i o n ~The ~ - ~product ~. of the reaction of Cu(I1) complexes of “tet b” with the thiosalicylate dianion affords crystals of the Cu(I1) t h i ~ l a t eAlso, ~ ~ . copper(I1) thiolates can be obtained from Cu(I1) salts with penicillamine dianion and related P-mercaptoamine~~’.
Penicillamine
R= [C6H4(2-C02)]6
7
With attention to both anionic and cationic counterions, a family of deeply colored, ~ )be~ ~ obtained, C ~ ] ~ as , well as mixed-valence compounds, [ C U ~ ~ ( S C R ~ C R ~ N Hcan related species wherein the cube of eight Cu(1) centers is replaced with Ag(1) or Au(1) and the six Cu(I1) sites are replaced by Ni(I1) or Pd(II)56.These complexes illustrate the ability of coordinated mercaptides to function as bridging ligands; simpler representatives of this effect are shown in 8 and 957358. 2-
H2N,
Ni
,S-Au-S
\
P q
H2N’
‘S-Au-S’
‘NH2
-o*c 8
.”H2 Ni
co;
9
While there exist few gold(II1) thiolates, 1,2-dithioleneligands stabilize these unusual species. Green [ A U ( ~ , ~ - S ~ C ~ H ~isCprepared H ~ ) ~ ] from reaction of Na2S2C6H3CH3 with [AuC14]- and is obtained as the crystalline [Bu,N]+ salt59. As with other dlO-species,the preparative chemistry of Zn and Cd thiolates depends on dynamic solution equalibria and the choice of solvent and counterions. Zinc salts react with mercaptides in nonaqueous solution to give (Ph,P),[M(SPh),] (M = Zn, Cd)60,catena-Zn(SPh),(ROH)I6’, (Me4N)2[Zn4(SPh)lo]62, and [Zn8Cl(SPh)16]61.Similarly, [Zn4(SPh)lo]2- has been synthesized electrochemically63. [Zn4(SPh)lo]2- was reacted with [MoS4I2-, yielding [Zn2(SPh)6]2-, but was more rationally synthesized using Z ~ I ( N Oand ~ ) ~[PPh,] [SPhI6,. Related Cd complexes are isolated and
26
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.6 From Sulfur Containing Anions (S*- , S$-, [HS - 1, [RS] - )
characterized, including [Cd(SR)2],, [Cd(SPh)41z-, [Cds(SR)1~II3 +,and [Cdlo(SR)16]4+ (R = SCHzCH20H)65-6s. Compounds [S4Cd17(SPh)2s]2-and [SCds(SPh)16]2- are prepared with C d 2 + salts and NaSPh and Na2S69,70. Additionally, (Me4N)2M4(SPh)10 (M = Zn, Cd) reacts with sulfur in MeCN, giving (Me4N)4[MloS4(SPh)16]as colorless crystals”. Structurally these resemble sphalerite (ZnS). The [CdloS4(SPh),,] is formed by heating (Me4N)4[CdloS4(SPh)16]to 250°C. Continued heating to 500°C eliminates Ph2S, yielding CdS. Dissolution in pyridine of the intermediate [Cdl0S4(SPh),,], and subsequent addition of D M F creates a magnificent pale yellow cubic cluster Cd32S14(SPh)36. DMF4, which combines a sphalerite lattice and wurtzitelike CdS units”. Reactions of Zn with heterocyclic mercaptides such as 2-mercaptobenzimidazole are relevant to rubber vulcanization catalysis; [Zn(SR),], and Na[Zn(SR),O,CR’] form73. Mercury(I1) mercaptides, Hg(SR),, are prepared by metathesis, e.g., from Hg(NO3)z. They are insoluble and are used in organic analysis and ~ y n t h e s i s ’ ~ ~Anionic ’~. complexes have been prepared by reaction of HgO with NaSPh76. (P. F. BRANDT, T. B. RAUCHFUSS) 1. N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, Pergamon Press, New York,
1984. R. T. Sanderson, Inorganic Chemistry, Reinhold, New York, 1967, p. 254. F. A. Cotton, G. Wilkinson, Adoanced Inorganic Chemistry, Wiley, New York, 1988. H. Schmidbauer, Angew. Chem., Int. Ed. Engl., 15, 728 (1976). T. Chivers, C. Lau, Inorg. Chem., 21, 453 (1982). G. Gattow, 0. Rosenberg, Z . Anorg. Allg. Chem., 332, 269 (1964). S. Haradem, J. L. Cronin, R. A. Krause, L. Katz, Inorg. Chim. Acta, 25, 173 (1977). C. Burschka, Z . Naturforsch., Teil B, 35, 1511 (1980). A. Miiller, U. Schimanski, Inorg. Chim. Acta, 77, L187 (1983). A. Miiller, F.-W. Baumann, H. Bogge, M. Romer, E. Krickemeyer, K. Schmitz, Angew. Chem., Int. Ed. Engl., 23, 632 (1984). 11. A. Miiller, M. Romer, H. Bogge, E. Krickemeyer, K. Schmitz, Inorg. Chim. Acta, 85, L39 (1984). 12. A. Miiller, M. Romer, H. Bogge, E. Krickemeyer, D. Bergmann, J . Chem. Soc., Chem. Commun., 348 (1984). 13. A. Miiller, F. W. Baumann, H. Bogge, K. Schmitz, Z . Anorg. Allg. Chem., 521, 89 (1985). 14. A. Miiller, H. Schlanderbeck, E. Krickemeyer, H. Bogge, K. Schmitz, E. Bill, A. X. Trautwein, Z . Anorg. Allg. Chem., 570, 7 (1989). 15. E. Ramli, T. B. Rauchfuss, C. L. Stern, J . Am. Chem. Soc., 112, 4043 (1990). 16. D. M. Young, G. L. Schimek, J. W. Kolis, Inorg. Chem., 35, 7620 (1996). 17. M. G. Kanatzidis, Y. Park, J . Am. Chem. Soc., I l l , 3767 (1989). 18. C. C. Raymond, P. K. Dorhout, S. M. Miller, Z . Kristallogr., 210, 776 (1995). 19. P. Betz., B. Krebs, G. Henkel, Angew. Chem., Int. Ed. Engl., 23, 311 (1984). 20. G. Henkel, P. Betz, B. Krebs, J . Chem. Soc., Chem. Commun., 314 (1984). 21. K. S. Nanjundaswamy, N. Y. Vasanthacharyaa, J. Gopalakrishnan, C. N. R. Rao, Inorg. Chem., 26, 4286 (1987). 22. A. Miiller, E. Krickemeyer, M. Zimmermann, M. Romer, H. Bogge, M. Penk, K. Schmitz, Inorg. Chim. Acta, 90, L69 (1984). 23. A. Miiller, M. Romer, H. Bogge, E. Krickemeyer, F.-W. Baumann, K. Schmitz, Inorg. Chim. Acta, 89, L7 (1984). 24. P. T. Wood, W. T. Pennington, J. W. Kolis, Inorg. Chem., 33, 1556 (1994). 25. P. T. Wood, W. T. Pennington, J. W. Kolis, J . Chem. Soc., Chern. Commun., 235 (1993). 26. F. E. Senftle, D. B. Wright, Z . Naturforsch., Teil B, 41, 1081 (1986). 27. G. Brauer. Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1963, p. 1063. 28. G. Marbach, J. Strahle, Angew. Chem., Int. Ed. Engl., 23, 246 (1984). 2. 3. 4. 5. 6. 7. 8. 9. 10.
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 27 3.7.3 Formation of the Bond Between Sulfur and a Group IB or llB Element 3.7.3.6 From Sulfur Containing Anions (S2-, S:-, [HS-1, [RS] - ) 29. D. Coucouvanis, P. R. Patil, M. G. Kanatzidis, B. Detering, N. C. Baenziger, Inorg. Chem., 24,24 (1985). 30. S. Dev, E. Ramli, T. B. Rauchfuss, C. L. Stern, J . Am. Chem. Soc., 112, 6385 (1990). 31. A. Muller, J. Schimanski, U. Schimanski, Angew. Chem., Int. Ed. Engl., 23, 159 (1984). 32. A. K. Verma, T. B. Rauchfuss, S. R. Wilson, Inorg. Chem., 34, 3072 (1995). 33. I. G. Dance, K. J. Fisher, G. D. Willett, Inorg. Chem., 35, 4177 (1996). 34. W. Beck, K. H. Stetter, S. Tadros, K. E. Schwarzhaus, Chem. Ber., 100, 3944 (1967). 35. G. A. Bowmaker, L.-C. Tan, Aust. J . Chem. 32, 1443 (1979). 36. D. Coucouvanis. C. N. Muruhv, S.K. Kanodia. Inorq. Chem., 19, 2993 (1980). 37. V. Vortisch, P. Kroneck, P. Hdmmerich, J . Am. Chem. Soc., 98, 2821 (1976). 38. W. Hirpo, S.Dhingra, M. G. Kanatzidis, J . Chem. Soc., Chem. Commun., 557 (1992). 39. W. Hirpo, S.Dhingra, A. Sutorik, M. G. Kanatzidis, J . Am. Chem. Soc., 115, 1597 (1993). 40. 0. Yang, K. Tang, H. Liao, Y. Han, Z. Chen, Y. Tang, J . Chem. Soc., Chem. Commun., 1076 (1987). 41. P. G. Eller, G. J. Kubas, J . Am. Chem. Soc., 99, 4346 (1977). 42. I. G. Dance, Inorg. Chim. Acta, 25, L17 (1977). 43. I. G. Dance, Aust. J . Chem., 31, 2195 (1978). 44. I. G. Dance, Inorg. Chem., 20, 1487 (1981). 45. K. Tang, M. Aslam, E. Block, T. Nicholson, J. Zubieta, Inorg. Chem., 24, 1488 (1987). 46. P. J. Sadler, Adz. Inorg. Chem. 34, l(1991). 47. A. Sladek, K. Angermaier, H. Schmidbauer, J . Chem. Soc., Chem. Commun., 1959 (1996). 48. G. H. Posner, in Organic Synthesis Collection, R. Adams, W. Reifschneider, A. Ferretti, eds., vol. 107, Wiley; New York, 1980. 49. G. N. Schrauzer, H. Prakash, Inorg. Chem., 14, 1201 (1975). 50. G. Henkel, B. Krebs, P. Betz, H. Fietz, K. Saatkamp, Angew. Chem., Int. Ed. Engl., 27, 1326 (1987). 51. A. R. Amundsen, J. Whelan, B. Bosnich. J . Am. Chem. Soc., 99, 6730 (1977). 52. J. S.Thompson, T. J. Marks, J. A. Ibers, J . Am. Chem. Soc., 101, 4180 (1979). 53. J. M. Downes, J. M. Whelan, B. Bosnich, Inorg. Chem., 20, 1081 (1981). 54. J. L. Hughey, T. G. Fawcett, S. M. Rudlich, R. A. Lalancette, J. A. Potenza, H. T. Schugar, J . Am. Chem. Soc., 101, 2617 (1979). 55. P. J. M. W. L. Birker, H. C. Freeman, J . Am. Chem. Soc., 99, 6890 (1977). 56. P. J. M. W. L. Birker, J. Reedijk, G. C. Verschoor, Inorg. Chem., 20, 2877 (1981). 57. M. J. Heeg, R. C. Elder, E. Deutsch, Inorg. Chem., 19, 554 (1980). 58. P. J. M. W. L. Birker, G. C. Verschoor, Inorg. Chem., 21, 990 (1982). 59. M. A. Mazid, M. T. Razi, P. J. Sadler, Inorg. Chem., 20, 2872 (1981). 60. D. Swenson, N. C. Baenziger, D. Coucouvanis, J . Am. Chem. Soc., 100, 1933 (1978). 61. I. G. Dance, J . Chem. SOC., Chem. Commun., 818 (1980). 62. I. G. Dance, J . Am. Chem. Soc., 101, 6264 (1979). 63. J. L. Hencher, M. A. Khan, F. F. Said, D. G. Tuck, Polyhedron, 4, 1263, (1985). 64. I. L. Abrahams, C. D. Garner, W. Clegg, J . Chem. Soc., Dalton Trans., 1577 (1987). 65. P. Strickler, J . Chem. Soc., Chem. Commun., 655 (1969). 66. H. B. Burgi, Helc. Chim. Acta, 57, 513 (1974). 67. H. B. Biirgi, H. Gehrer, P. Strickler, F. K. Winkler, Helt.. Chim. Acta, 59, 2558 (1976). 68. D. Coucouvanis, C. N. Murphy, E. Simhon, P. Stremple, M. Draganjac, Inorg. Synth., 21, 23 (1982). 69. G. S. H. Lee, D. C. Craig, I. Ma, M. L. Scudder, T. D. Bailey, I. G. Dance, J . Am. Chem. SOC.,110, 4863 (1988). 70. G. S. H. Lee, K. J. Fisher, D. C. Craig, M. L. Scudder, I. G. Dance, J . Am. Chem. Soc., 112,6435 (1990). 71. I. G. Dance, A. Choy, M. Scudder, J . Am. Chem. Soc., 104, 6285 (1984). 72. N. Herron, J. C. Calabrese, W. E. Farneth, Y. Wang, Science, 259, 1426 (1993). 73. J. A. McCleverty, N. Spencer, N. A. Bailey, S.S.Shackleton, J . Chem. Soc., Dalton Trans., 1939 (1980). 74. E. E. Reid, Organic Chemistrj ofBicalent Sulfur, Vol. 1, Chemical Publishing, New York, 1958, Ch. 2. 75. D. P. M. Satchell, Chem. Soc. Rec.; 6, 345 (1977). 76. G. Christou, K. Folting, J. C. Huffman, Polyhedron, 3, 1247 (1984). ,
"
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
28
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.1 Formation of the Bond with Selenium
3.7.3.7 By Metal Atom and Related Reactions
Microscale codeposition of Ag atoms with SiS vapor was reported; in solid Ar the structure of the Ag SiS adduct is probably triangular'. (K. J. KLABUNDE) 1. J. A. Howard, R. Jones, J. S. Tse, M. Tomietto. P. L. Timms, A. J. Seeley, J . Phys. Chem., 96,9144
(1992).
3.7.4 Formation of the Bond Between Selenium, Tellurium, and Polonium and Group IB or llB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.1 Formation of the Bond with Selenium
The monoselenides and -tellurides of Zn and Cd are important semiconductors that find many applications in photoelectric devices; their synthesis has been extensively studied, as have the phase diagrams of the components',2. Table 1 lists the selenides and tellurides that can be prepared by direct reaction between the elements'-30. Extensive studies on the Zn-Se system show that the system components do not mix in the liquid state'Sl6. If Zn and Se are mixed in a quartz ampule, solid ZnSe is formed only at the boundary of the liquid phases. Thus ZnSe is not normally prepared by direct reaction between the elements, although single crystals of the material have been prepared in this way, in very low yields3. Similarly Cd and Se are almost insoluble in each other in the liquid state'; a solidified mixture of the two molten elements yields only two layers, separated by an interlayer of CdSe. Thermal methods have been used to synthesize CdSe from the elements, but the product is generally of variable composition3133 2 . A recent report claims formation of single crystals of CdSe from reaction between Cd and Se vapors in Ar at 1050-1070°C32. Mercury selenide can be obtained from reaction of stoichiometric quantities of Hg and Se in an evacuated quartz a m p ~ l ealthough ~ ~ ~ there ~ ~ ~are, aqueous methods for its preparation, generally starting from Hg(I1) salts. The elements react in acidic aqueous solution if they are first dissolved separately in H N 0 3 . Then (NH4),S03 is added to the combined solutions, the product is heated to 90°C and acidified with acetic acid. Black powdered HgSe forms which is washed with H 2 0 and MeOH and allowed to dry at 95"C*. The diselenides of Zn and Cd have been prepared at high pressures34. The compounds have pyrite structures and show semiconducting behavior. The affinity of Se for elements of group IB decreases from Cu to Au. There are several well-established selenides of copper, but no stable gold selenides. The Cu-Se system has been s t ~ d i e d ~ ~and - ~ various ', selenides of copper are apparent, (e.g., Cu2Se, Cu3Se2,CuSe, CuSe,). These are obtained by melting together equimolar quantities of Se and Cu in evacuated quartz ampules at temperatures a little above the melting point. The reactions occurring are largely exothermic, and to prevent explosion of the ampules, the temperature must be held at 250-350°C for no less than 1 h before being gradually increased to the melting point'. If Cu and Se are heated in a 2: 1 molar ratio, Cu,Se alone forms".
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
28
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.1 Formation of the Bond with Selenium
3.7.3.7 By Metal Atom and Related Reactions
Microscale codeposition of Ag atoms with SiS vapor was reported; in solid Ar the structure of the Ag SiS adduct is probably triangular'. (K. J. KLABUNDE) 1. J. A. Howard, R. Jones, J. S. Tse, M. Tomietto. P. L. Timms, A. J. Seeley, J . Phys. Chem., 96,9144
(1992).
3.7.4 Formation of the Bond Between Selenium, Tellurium, and Polonium and Group IB or llB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.1 Formation of the Bond with Selenium
The monoselenides and -tellurides of Zn and Cd are important semiconductors that find many applications in photoelectric devices; their synthesis has been extensively studied, as have the phase diagrams of the components',2. Table 1 lists the selenides and tellurides that can be prepared by direct reaction between the elements'-30. Extensive studies on the Zn-Se system show that the system components do not mix in the liquid state'Sl6. If Zn and Se are mixed in a quartz ampule, solid ZnSe is formed only at the boundary of the liquid phases. Thus ZnSe is not normally prepared by direct reaction between the elements, although single crystals of the material have been prepared in this way, in very low yields3. Similarly Cd and Se are almost insoluble in each other in the liquid state'; a solidified mixture of the two molten elements yields only two layers, separated by an interlayer of CdSe. Thermal methods have been used to synthesize CdSe from the elements, but the product is generally of variable composition3133 2 . A recent report claims formation of single crystals of CdSe from reaction between Cd and Se vapors in Ar at 1050-1070°C32. Mercury selenide can be obtained from reaction of stoichiometric quantities of Hg and Se in an evacuated quartz a m p ~ l ealthough ~ ~ ~ there ~ ~ ~are, aqueous methods for its preparation, generally starting from Hg(I1) salts. The elements react in acidic aqueous solution if they are first dissolved separately in H N 0 3 . Then (NH4),S03 is added to the combined solutions, the product is heated to 90°C and acidified with acetic acid. Black powdered HgSe forms which is washed with H 2 0 and MeOH and allowed to dry at 95"C*. The diselenides of Zn and Cd have been prepared at high pressures34. The compounds have pyrite structures and show semiconducting behavior. The affinity of Se for elements of group IB decreases from Cu to Au. There are several well-established selenides of copper, but no stable gold selenides. The Cu-Se system has been s t ~ d i e d ~ ~and - ~ various ', selenides of copper are apparent, (e.g., Cu2Se, Cu3Se2,CuSe, CuSe,). These are obtained by melting together equimolar quantities of Se and Cu in evacuated quartz ampules at temperatures a little above the melting point. The reactions occurring are largely exothermic, and to prevent explosion of the ampules, the temperature must be held at 250-350°C for no less than 1 h before being gradually increased to the melting point'. If Cu and Se are heated in a 2: 1 molar ratio, Cu,Se alone forms".
3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.1 Formation of the Bond with Selenium
29
TABLE1. FORMATION OF THE BONDBETWEEN Se, Te, AND GROUP IB AND IIB ELEMENTS BY DIRECT REACTION
Compound Zn
Elements
Reaction Type Vapor state in Ar Liquid NH, Vapor state in Ar Liquid NH, Heat in ampule Heat in ampule HNO, solution Heat in quartz tube Flow reaction using Se vapor in N, Heat in sealed tube Surface diffusion of Se into Cu In CuSO, solution Melt Vapor Liquid NH, Melt Melt in temperature gradient Melt in quartz tube In HNO,/HCl solution Melt High pressure Melt under NaCI/KCI Pass Te vapor over Ag Melt Melt
ZnSe ZnSe CdSe CdSe HgSe HgSe HgSe CuSe Cu,Se
Cd Cd Hg Hg Hg Cu Cu
Se Se Se Se Se Se Se Se Se
Cu,Se Cu,Se
Cu Cu
Se (2: 1) Se
Cu2Se Ag,Se Ag,Se ZnTe CdTe
Cu Ag Ag Ag Zn Cd
Se Se Se Se Te Te
HgTe HgTe CuTe CuTe, Cu,Te Ag,Te Ag,Te Ag,Te
Hg Hg Cu Cu Cu Ag Ag Ag
Te Te Te Te Te Te Te Te
Zn
Temperature ("C)
Time (h)
RT 1050-1070 RT 800 683 90 250-350 300400 gradient
2-12 2-12 0.5
Ref.
3, 4 15 5 15 1, 6 7 8 9 9 10 11
1050 300400 RT 1300 550-750
15-20 6-8 2-12
700-720
1,2
470 600 800
12 1, 9, 13 14 15 2, 15, 16, 17 2, 18-20 15, 21 22 2 23 10,24 25,26 21,28 29, 30
Crystals of Cu2Se are obtained by passing Se vapor, carried by N2 or Ar, over the surface of Cu heated to 400"C37.Cu2Se is also formed by surface diffusion of Se vapor into Cu in the [ l l O ] direction". Silver forms only one stoichiometric compound with Se: Ag2Se is obtained by melting the elements in evacuated quartz ampules at ca. 1050'C and holding the melt for 15-20 h. To prevent reduction of the silver by light, the ampules must be coated with graphite'~'~.Good samples of Ag2Se have been reported by a flow method in which Se vapor in N2 or Ar is passed over the surface of silver shavings at 400°C for 6-8 h. When absorption of Se is complete, the product is heated in vacuo for several hours to drive off excess Se9314. Ag,Se is diamagnetic, shows semiconducting properties, and exists in more than one modification. The RT form has an ordered orthorhombic structure; the high temperature form has atoms distributed over many positions in a body-centered-cubic (bcc) lattice.
30
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.1 By Reaction with the Group IB or IIB Metals 3.7.4.1.2 Formation of the Bond with Tellurium
Maximum solubility of Se in Au at 1020°C is 5.2%. Only one compound, AuSe, was found in the gold-selenium system4. It exists in a stable metallic form up to 698 K and is metastable above this temperature3'. (E. M. PAGE) 1. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 2. D. M. Chizikov, V. P. Shchastlivyi, Tellurium and Tellurides, Collets, London, 1970. 3. A. Pashinkin, G. N. Tishchenko, G. N. Konyaeva, E. V. Ryzhenko, Kristallografika, 5, 261 (1960). 4. F. Jellinek, Sulphides, Selenides and Tellurides of Transition Elements, in M T P International Reviews ofScience, Part 1, H. J. Emeleus, A. G. Sharpe, eds., Butterworths, London, 1960. 5. N. I. Vitrikhovskii, I. B. Mizetskaya, Fiz. Tuerd. Tela, 3, 1581 (1961). 6. A. V. Golubov, P. V. Usachev, N. S . Volosatova, Zh. Prikl. Khim., 33, 277 (1960). 7. F. M. Climent Montoliu, P. Ruiz-Dana Capmany, J. L. Rodriguez-Lopez,An. Quim., Ser. B, 78, 387 (1982). Chem. Abstr., 98, 118427. 8. P. V. Usachev, Zh. Prikl. Khim., 33, 2271 (1960). 9. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 10. P. Rahlfs, Z . Phys. Chem., B, 31, 157, (1936). 11. V. I. Arkharov, Dokl. Akad. Nauk, SSSR, 95, 517 (1954). 12. L. Moser, K. Atynski, Monatsh. Chem., 45, 235 (1925). 13. G. A. Akhundov, G. B. Abdulaev, M. Kh. Alimov, Vopr. Met. Fiz. Poluproc, Akad. Nauk SSSR, 104 (1961). 14. 0. Honigschmid, W. Kapfenberger, Z . Anorg. Chem., 212, 198 (1933). 15. G. Henshaw, I. P. Parkin, G. Shaw, J . Chem. Soc. Chem. Commun., 1095 (1996). 16. M. Chikashige, R. Kurasawa, Met. Coll. Sci. Kyoto Unit.., 2, 245 (1917). 17. M. V. Kot, V. G. Tyrziu, Uch. Zap. Kishinet. Unic., 55, 15 (1960). 18. T. R. Lynch, J . Appl. Phys., 33, 109 (1962). 19. P. Hosch, C. Konak, Czech. J . Phys., B13, 850 (1963). 20. K. Mori, T. Akiyoshi, Jpn. Kokai Tokyo Koho, J P , 60, 141,606 (1985); Japanese Patent 85, 141, 606; Chem. Abstr., 104, 53025 (1986). 21. M. Aven, W. Garwacki, J . Electrochem. Soc., 110, 401 (1963). 22. S. M. Kulifay, J . Am. Chem. SOC., 83, 4916 (1961). 23. T. A. Bither, C. T. Prewitt, J. L. Gillson, P. E. Bierstedt, R. B. Flippen, H. S. Young, Solid State Commun., 4, 533 (1966). 24. H. Nowotny, Z . Metallforsch, I , 40 (1946). 25. M. Aoki, I. Suge, J . Appl. Phys. Jpn., 15, 363 (1960). 26. 0. Honigschmid, Z . Anorg. Chem., 214, 281 (1933). 27. E. Zintl, J. Goubeau, W. Dullenkopf, 2. Phys. Chem., I , 154 (1931). 28. P. Rahlfs, Z . Phys. Chem., B, 31, 157, (1936). 29. P. Manca, F. J. Massazza, J . Appl. Phys., 33, 1608 (1962). 30. C. R. Veale, J . Less Common Met., 11, 50 (1966). 31. R. Schrader, S . Lasof, N. Leverez, The Preparation and Characterisation of Solid Luminescent Materials, Symposium, Oxford, 1948. 32. K. Huml, Cesk. Casopis Fiz, 11, 357 (1961). 33. G. Pellini, R. Sacerdoti, Gazz. Chim. Ital., 40, 11, 42 (1910). 34. T. A. Bither, R. J. Bouchard, W. H. Cloud, P. C. Donohue, W. J. Siemons, Inorg. Chem., 7,2208 (1968). 35. A. L. N. Stevels, F. Jellinek, Rel. Trau. Chim. Pays-Bas, 90, 273 (1971). 36. R. D. Heyding, Can. J . Chem., 44, 1233 (1966). 37. H. Rau, A. Rabenau, J . Solid State Chem., I , 515 (1970). 38. A. Rabenau, H. Rau, G. Rosenstein, J . Less Common Met., 24, 291 (1971).
3.7.4.1.2 Formation of the Bond with Tellurium
Formation of many heavy metal tellurides by direct reaction between the elements was originally reported in the nineteenth centurylS2.ZnTe, HgTe, and CuzTe were first
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
30
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.1 By Reaction with the Group IB or IIB Metals 3.7.4.1.2 Formation of the Bond with Tellurium
Maximum solubility of Se in Au at 1020°C is 5.2%. Only one compound, AuSe, was found in the gold-selenium system4. It exists in a stable metallic form up to 698 K and is metastable above this temperature3'. (E. M. PAGE) 1. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 2. D. M. Chizikov, V. P. Shchastlivyi, Tellurium and Tellurides, Collets, London, 1970. 3. A. Pashinkin, G. N. Tishchenko, G. N. Konyaeva, E. V. Ryzhenko, Kristallografika, 5, 261 (1960). 4. F. Jellinek, Sulphides, Selenides and Tellurides of Transition Elements, in M T P International Reviews ofScience, Part 1, H. J. Emeleus, A. G. Sharpe, eds., Butterworths, London, 1960. 5. N. I. Vitrikhovskii, I. B. Mizetskaya, Fiz. Tuerd. Tela, 3, 1581 (1961). 6. A. V. Golubov, P. V. Usachev, N. S . Volosatova, Zh. Prikl. Khim., 33, 277 (1960). 7. F. M. Climent Montoliu, P. Ruiz-Dana Capmany, J. L. Rodriguez-Lopez,An. Quim., Ser. B, 78, 387 (1982). Chem. Abstr., 98, 118427. 8. P. V. Usachev, Zh. Prikl. Khim., 33, 2271 (1960). 9. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 10. P. Rahlfs, Z . Phys. Chem., B, 31, 157, (1936). 11. V. I. Arkharov, Dokl. Akad. Nauk, SSSR, 95, 517 (1954). 12. L. Moser, K. Atynski, Monatsh. Chem., 45, 235 (1925). 13. G. A. Akhundov, G. B. Abdulaev, M. Kh. Alimov, Vopr. Met. Fiz. Poluproc, Akad. Nauk SSSR, 104 (1961). 14. 0. Honigschmid, W. Kapfenberger, Z . Anorg. Chem., 212, 198 (1933). 15. G. Henshaw, I. P. Parkin, G. Shaw, J . Chem. Soc. Chem. Commun., 1095 (1996). 16. M. Chikashige, R. Kurasawa, Met. Coll. Sci. Kyoto Unit.., 2, 245 (1917). 17. M. V. Kot, V. G. Tyrziu, Uch. Zap. Kishinet. Unic., 55, 15 (1960). 18. T. R. Lynch, J . Appl. Phys., 33, 109 (1962). 19. P. Hosch, C. Konak, Czech. J . Phys., B13, 850 (1963). 20. K. Mori, T. Akiyoshi, Jpn. Kokai Tokyo Koho, J P , 60, 141,606 (1985); Japanese Patent 85, 141, 606; Chem. Abstr., 104, 53025 (1986). 21. M. Aven, W. Garwacki, J . Electrochem. Soc., 110, 401 (1963). 22. S. M. Kulifay, J . Am. Chem. SOC., 83, 4916 (1961). 23. T. A. Bither, C. T. Prewitt, J. L. Gillson, P. E. Bierstedt, R. B. Flippen, H. S. Young, Solid State Commun., 4, 533 (1966). 24. H. Nowotny, Z . Metallforsch, I , 40 (1946). 25. M. Aoki, I. Suge, J . Appl. Phys. Jpn., 15, 363 (1960). 26. 0. Honigschmid, Z . Anorg. Chem., 214, 281 (1933). 27. E. Zintl, J. Goubeau, W. Dullenkopf, 2. Phys. Chem., I , 154 (1931). 28. P. Rahlfs, Z . Phys. Chem., B, 31, 157, (1936). 29. P. Manca, F. J. Massazza, J . Appl. Phys., 33, 1608 (1962). 30. C. R. Veale, J . Less Common Met., 11, 50 (1966). 31. R. Schrader, S . Lasof, N. Leverez, The Preparation and Characterisation of Solid Luminescent Materials, Symposium, Oxford, 1948. 32. K. Huml, Cesk. Casopis Fiz, 11, 357 (1961). 33. G. Pellini, R. Sacerdoti, Gazz. Chim. Ital., 40, 11, 42 (1910). 34. T. A. Bither, R. J. Bouchard, W. H. Cloud, P. C. Donohue, W. J. Siemons, Inorg. Chem., 7,2208 (1968). 35. A. L. N. Stevels, F. Jellinek, Rel. Trau. Chim. Pays-Bas, 90, 273 (1971). 36. R. D. Heyding, Can. J . Chem., 44, 1233 (1966). 37. H. Rau, A. Rabenau, J . Solid State Chem., I , 515 (1970). 38. A. Rabenau, H. Rau, G. Rosenstein, J . Less Common Met., 24, 291 (1971).
3.7.4.1.2 Formation of the Bond with Tellurium
Formation of many heavy metal tellurides by direct reaction between the elements was originally reported in the nineteenth centurylS2.ZnTe, HgTe, and CuzTe were first
3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.1 By Reaction with the Group IB or IIB Metals 3.7.4.1.2 Formation of the Bond with Tellurium
31 ~~
prepared in this way. Recently, the reactions have been studied much further, as have the metal-tellurium phase diagrams. Reaction between Te and Zn in the melt at 1300°C yields crystals of ZnTe with opaque inclusions of Te2-4. Although the excess Te can be removed by heating at llOOcC in an atmosphere of He and ZnTe vapor, the Te appears again after cooling. Direct reaction between Cd and Te yields CdTe. Numerous methods are known for production of crystals of CdTe, and most involve synthesis of CdTe vapor from the elements in a temperature gradient followed by crystallization of the vapor in a current of inert Fine pure CdTe can be prepared in silica apparatus at lower temperatures (550-750T) for extended times'. Mercury(I1) telluride is an unstable solid, obtained by melting together the elements in Hg vapor at 700-720"C2~8.Extreme care should be taken to prevent explosion by using a thick-walled (3-5 mm) quartz tube and a very gradual temperature increase ( 2100Whr). HgTe can be prepared relatively rapidly by vapor phase synthesis. Here Te is held close to the melting point of HgTe and the Hg is held at 550°C. An aqueous method has been reported for preparation of several group IB and IIB tellurides, starting from the metal or metal salt'. In reaction to produce HgTe, Hg is first dissolved in hot concentrated nitric and hydrochloric acids and a solution of Te in aqua regia is added. The solution is reduced using N 2 H 4 .2HC1 and N H 4 0 H , yielding 98.8% crystalline HgTe. The synthesis is rapid and convenient, since it uses temperatures of around 100°C and atmospheric pressure. Various silver tellurides have been prepared similarly starting from AgNO, in aqueous solution. Reaction of Cu with Te yields tellurides CuzTe, Cu4Te3, and CuTe, along with various nonstoichiometric compounds'.''. CuzTe is obtained by fusing electrolytic Cu with pure Te in a crucible under a protective layer of NaCl and KCI".'2. Cu4Te3 and CuTe are prepared similarly, using the respective stoichiometric quantities, but the composition of both tellurides depends on T. Reaction of metallic Ag with Te at temperatures above 470°C yields Ag,Te. Reaction can be carried out either by passing Te vapor with a carrier such as H 2 over Ag at 470CC2,11,13,14or by melting the components in an evacuated quartz tube above 600"C15-'7. Both products contain excess Te, which is removed by heating in vacuo. A review on silver tellurium compounds has been published". The Ag-Te system has been extensively studied' and various nonstoichiometric phases reported, one of which conforms to Ag7Te4. The compound AgTe, the mineral empressite, has not been synthesized. The only stable compound obtained from reaction between Au and Te is A U T ~ ~ ~ ~ ~ ' , which occurs in nature as the minerals calaverite and krennerite. The existence of AuzTe has not been confirmed; Au2Te3is unstable. A convenient, low energy synthesis of metal selenides, (Ag'Se, ZnSe, CdSe) was reported, involving reaction of the elemental metal with Se in liquid NH, at RT in a thick-walled Teflon-in-glass pressure tube for up to 12 hZ1. Caution: Such reactions in liquid NH3 at room temperature have been known to explode. All reactions should be conducted behind a safety screen with blastproof netting around reaction vessels. (E. M. PAGE) 1. D. M. Chizikov and V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 2. D. M. Chizikov, V. P. Shchastlivyi, Tellurium and Tellurides, Collets, London, 1970.
32
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.3 Electrolytic Reactions Between the Elements
M. Chikashige and R. Kurasawa, Met. Coll. Sci. Kyoto Uniu., 2, 245 (1917). M. V. Kot, V. G. Tyrziu, Uch. Zap. Kishinec. Unio., 5.5, 15 (1960). T. R. Lynch, J . Appl. Phys., 33, 109 (1962). P. Hosch, C. Konak, Czech. J . Phys., B, 13, 850 (1963). K. Mori, T. Akiyoshi, Jpn. Kokai Tokyo Koho, JP, 60, 141,606; {Japanese Patent 85, 141,606} Chem. Abst., 104: 53025 (1986). 8. M. Aven, W. Garwacki, J. Electrochem. Soc., 110, 401 (1963). 9. S. M. Kulifay, J . Am. Chem. Soc., 83, 4916 (1961). 10. 0. Honigschmid and W. Kapfenberger, Z . Anorg. Chem., 212, 198 (1933). 11. G. Brauer, Handbook of Preparative Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 12. H. Nowotny, Z . Metallforsch, I , 40 (1946). 13. M. Aoki, I. Suge, J . Appl. Phys. Jap., 15, 363 (1960). 14. 0. Honigschmid, 2. Anorg. Chem., 214, 281 (1933). 15. E. Zintl, J. Goubeau, W. Dullenkopf, Z . Phys. Chem., I , 154 (1931). 16. P. Rahlfs, 2. Phys. Chem., B, 31, 157 (1936). 17. P. Manca, F. J. Massazza, J . A p p l . Phys., 33, 1608 (1962). 18. C. R. Veale, J . Less Common Met., 11, 50 (1966). 19. F. C. Kracek, C. J. Ksanda, L. J. Cabri, Am. Miner., 31, 14 (1966). 20. L. J. Cabri, Econ. Geol., 60, 1569 (1965). 21. G. Henshaw, I. P. Parkin, G. Shaw, J . Chem. Soc., Chem. Commun., 1095 (1996). 3. 4. 5. 6. 7.
3.7.4.1.3 Electrolytic Reactions Between the Elements
Direct reaction between the elements is the most common method for preparation of group IB and IIB tellurides. These reactions require high temperatures and, as the compounds cool, the electronic systems attain equilibrium at room temperature. Motion of lattice defects and diffusion of atoms is very slow below about 1.5 times the melting temperature. Such high temperature syntheses yield high concentrations of lattice defects and variable chemical compositions. Also, the high temperatures required for reaction and the high vapor pressures encountered are inconvenient and result in peritectic reactions. Electrolytic reactions provide a convenient low temperature route to several heavy metal tellurides'. Telluride ions are produced by cathodic dissolution of Te in acid solution (NH40H/AcOH). Metal ions are introduced by simultaneous anodic dissolution of the metal: a current is passed between a Te cathode and a metal anode through an acidic electrolyte. The electrodes dissolve cleanly; tellurides are formed by ionic reaction in the solution. When metal ions cannot be produced by anodic dissolution, they are added as salt solutions. Acidic media are necessary because at higher pH values reaction occurs between the ditelluride and metal ions causing contamination of the product with Te according to the equation: M"
+ Te$--+
MTe
+ Te
(a)
The precipitates obtained are very fine particles having broad X-ray patterns; the particle size can be increased by boiling for 16 h. CuTe and ZnTe are obtained in high yields from reaction of this type. These tellurides are difficult to prepare by other methods because CuTe suffers a peritectic reaction at 367"C, and ZnTe requires an extremely high temperature for its preparation by heating the elements. AgzTe and ZnTe were also prepared by an electrolytic reaction using the salts AgN03 and ZnC12 as the source of metal ions. (E. M. PAGE) 1. A. J. Panson, Inorg. Chem., 3, 940 (1964).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
32
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.1 By Reaction with the Group IB or llB Metals 3.7.4.1.3 Electrolytic Reactions Between the Elements
M. Chikashige and R. Kurasawa, Met. Coll. Sci. Kyoto Uniu., 2, 245 (1917). M. V. Kot, V. G. Tyrziu, Uch. Zap. Kishinec. Unio., 5.5, 15 (1960). T. R. Lynch, J . Appl. Phys., 33, 109 (1962). P. Hosch, C. Konak, Czech. J . Phys., B, 13, 850 (1963). K. Mori, T. Akiyoshi, Jpn. Kokai Tokyo Koho, JP, 60, 141,606; {Japanese Patent 85, 141,606} Chem. Abst., 104: 53025 (1986). 8. M. Aven, W. Garwacki, J. Electrochem. Soc., 110, 401 (1963). 9. S. M. Kulifay, J . Am. Chem. Soc., 83, 4916 (1961). 10. 0. Honigschmid and W. Kapfenberger, Z . Anorg. Chem., 212, 198 (1933). 11. G. Brauer, Handbook of Preparative Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 12. H. Nowotny, Z . Metallforsch, I , 40 (1946). 13. M. Aoki, I. Suge, J . Appl. Phys. Jap., 15, 363 (1960). 14. 0. Honigschmid, 2. Anorg. Chem., 214, 281 (1933). 15. E. Zintl, J. Goubeau, W. Dullenkopf, Z . Phys. Chem., I , 154 (1931). 16. P. Rahlfs, 2. Phys. Chem., B, 31, 157 (1936). 17. P. Manca, F. J. Massazza, J . A p p l . Phys., 33, 1608 (1962). 18. C. R. Veale, J . Less Common Met., 11, 50 (1966). 19. F. C. Kracek, C. J. Ksanda, L. J. Cabri, Am. Miner., 31, 14 (1966). 20. L. J. Cabri, Econ. Geol., 60, 1569 (1965). 21. G. Henshaw, I. P. Parkin, G. Shaw, J . Chem. Soc., Chem. Commun., 1095 (1996). 3. 4. 5. 6. 7.
3.7.4.1.3 Electrolytic Reactions Between the Elements
Direct reaction between the elements is the most common method for preparation of group IB and IIB tellurides. These reactions require high temperatures and, as the compounds cool, the electronic systems attain equilibrium at room temperature. Motion of lattice defects and diffusion of atoms is very slow below about 1.5 times the melting temperature. Such high temperature syntheses yield high concentrations of lattice defects and variable chemical compositions. Also, the high temperatures required for reaction and the high vapor pressures encountered are inconvenient and result in peritectic reactions. Electrolytic reactions provide a convenient low temperature route to several heavy metal tellurides'. Telluride ions are produced by cathodic dissolution of Te in acid solution (NH40H/AcOH). Metal ions are introduced by simultaneous anodic dissolution of the metal: a current is passed between a Te cathode and a metal anode through an acidic electrolyte. The electrodes dissolve cleanly; tellurides are formed by ionic reaction in the solution. When metal ions cannot be produced by anodic dissolution, they are added as salt solutions. Acidic media are necessary because at higher pH values reaction occurs between the ditelluride and metal ions causing contamination of the product with Te according to the equation: M"
+ Te$--+
MTe
+ Te
(a)
The precipitates obtained are very fine particles having broad X-ray patterns; the particle size can be increased by boiling for 16 h. CuTe and ZnTe are obtained in high yields from reaction of this type. These tellurides are difficult to prepare by other methods because CuTe suffers a peritectic reaction at 367"C, and ZnTe requires an extremely high temperature for its preparation by heating the elements. AgzTe and ZnTe were also prepared by an electrolytic reaction using the salts AgN03 and ZnC12 as the source of metal ions. (E. M. PAGE) 1. A. J. Panson, Inorg. Chem., 3, 940 (1964).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.2 By Reaction with Group IB or IIB Metal Compounds 3.7.4.2.1 Binary Compounds
33
3.7.4.2 By Reaction with Group IB or IIB Metal Compounds 3.7.4.2.1 Binary Compounds
Table 1 lists reactions between elemental Se and Te and group IB and IIB metal compounds that yield metal-chalcogen bonds. However, this approach is not widely applicable for the formation of metal chalcogenides. Zinc iodide is a precursor to ZnSe and ZnTe in a flow reaction at 580°C'. ZnSe can also be prepared from a mixture of ZnO, ZnS, and Se as: 2Zn0
+ ZnS + 3Se-
3ZnSe + SOz
(a)
The mixture is heated at 800°C for 15 min in a quartz glass crucible'. When CdS and Se are heated together at 500°C, an exchange reaction occurs wherein CdSe is formed3. CdS
+ Se-
CdSe
+S
(b)
Equilibrium is established within 3-5 h at this temperature. HgO is readily reduced by Te to Hg, and if the temperature is not too high, HgTe forms. Similarly, CuzTe can be obtained from reaction between C u 2 0 and Te4. Tellurium will displace S from CuzS and AgzS at 500°C to give tellurides CuzTe and AgzTe. On fusion with AgNO,, Te gives a brown compound AgzTe03.AgN03 with the evolution of NOz. This can be converted to AgzTe upon heating5. TABLE1. BINARYCOMPOUNDS Product
Reactants
Reaction Type
Temperature
Ref.
("C)
ZnY (Y = Se, Te) ZnI, + Y ZnSe ZnO ZnS + Se CdSe CdS + Se HgTe HgO + Te HgY (Y = Se, Te) HgZ++ Y Cu,Se CuCl + Se(g) CuTe Cuz-(aq) + Te Cu,Te C u 2 0 + Te Cu,Te Cu,S + Te Cu,Y CU2+ + Y (Y = Se or Te) + Y in aqua regia AgN0, or AgF + CuSe AgSe AgNO, or AgCl + Y AB2Y (Y = Se or Te) Ag2Te AgNO, Te Ag2Te AgCl + Te Ag,Te Ag2S Te Ag2-J-e AgN03 + Te AgN03 + Te (2: 1) Ag2Te
+
~
Flow reaction Quartz crucible Heat Hg2' in HNO,
400
Heat Cu2+ in HNO,
+ Te (1 1 : 7 )
In NH,OH with NzH4 reductant In NH40H with N2H4 reductant
1
2 3
4 11 6 12 4 5 11 8 13
80 RT
+
AgNO,
500
Aqueous solution Hot aqueous solution
+
Ag11Te7
580 800 500 for 3-5 days
10 10 5 5 9 9
34
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.2 By Reaction with Group IB or IIB Metal Compounds 3.7.4.2.2 Ternary Compounds
~~
Solid copper salts can be used instead of crystalline Cu in a reaction with Se vapor at 400°C to yield Cu2Se6. Reaction of solutions of the Ag salts AgN03 and AgF with CuSe has been used to prepare Ag2Se13738. In a method mentioned earlier (see 3.7.4.1),various Ag tellurides have been prepared starting from AgN03 and re9. The method involves mixing together reactant solutions in the correct stoichiometry for the product with NH,OH(aq). The AgN03 can be used in aqueous solution, but Te must be dissolved in aqua regia. The resultant solution is then reduced using a mixture of N2H4.2HC1 and NH,OH, causing precipitation of the metal telluride in good yield. Similarly reaction of Se with Cu2+ or Ag+ solutions in NH3 yields products that approximate to Cu2Se and Ag2Se". Analogous reactions of Te with Cu2+solutions yield Cu2Te or CuTe depending on conditions. Reaction of Te with either AgCl or AgN03 in ammoniacal solution for prolonged periods precipitates Ag2Te. However, Te reduces AuCl solution to metallic Au irrespective of the reaction temperature. Whereas Se reduces Ag solutions when cold, it has no effect on Au solutions until almost boiling, at which point Au is precipitated. Selenides and tellurides of Hg and Cu are prepared by precipitation from solutions of selected metal salts in acidic solution". In the formation of HgTe, a solution of Te in aqua regia is added to Hg dissolved in H N 0 3 . The mixture is reduced by addition to a boiling solution of (NH4)2S03and acetic acid12. (E. M. PAGE) I. L. Karagiozov, E. Trifona, Cryst. Res. Techno/.,19, 447 (1984). 2. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 3. M. F. Banoch, P. Golebom, G. F. Hevenh, Acta Phys. Chem., Szeged, 4, 97 (1958). 4. E. Montignie, Ann. Pharm. Fr., I , 107 (1943); Chem. Abst., 40, 4307 (1946). 5. E. Montignie, Ann. Pharm. Fr., 4 , 251 (1946); Chem. Abst., 41, 6829 (1947). 6. L. Moser, K. Atynski, Monatsh. Chem., 45, 235 (1925). 7. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 8. W. Geilmann, W. Wrigge, Z. Anorg. Allg. Chem., 210, 378 (1933). 9. S. M. Kulifay, J . Am. Chem. Soc., 83, 4916 (1961). 10. R. D. Hall, V. Lenher, J . Am. Chem. Soc., 24, 918 (1902). 11. S. M. Kulifay, U. S. Patent 3026,175 (1962); Chem. Abst. 57, 267 (1962). 12. E. C. Parkman, Am. J . Sci., 2, 33, 328 (1862). 13. B. J. Aylett, in Comprehensice Inorganic Chemistry, Vol. 3, A. F. Trotman-Dickenson. ed., Pergamon Press, Oxford, 1973. p. 187. 3.7.4.2.2 Ternary Compounds
A general synthesis of Cu and Au chalcogenide halides in which M-Y bonds are formed (M = Cu: Au; Y = Se, Te) has been reported', and the syntheses have been reviewed2. Only sulfido halides are known for Ag whereas for Cu and Au there are reports of seleno- and tellurohalides only. Starting materials and conditions are listed in Table 11,3-10. Reaction occurs between the elemental chalcogen and binary group IB metal halide in the appropriate hydrohalic acid. The components are added to a silica ampule, which is sealed at liquid N2 temperature and allowed to warm slowly. Excessive pressures may develop, and a heavy face shield should be worn during this reaction.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
34
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.2 By Reaction with Group IB or IIB Metal Compounds 3.7.4.2.2 Ternary Compounds
~~
Solid copper salts can be used instead of crystalline Cu in a reaction with Se vapor at 400°C to yield Cu2Se6. Reaction of solutions of the Ag salts AgN03 and AgF with CuSe has been used to prepare Ag2Se13738. In a method mentioned earlier (see 3.7.4.1),various Ag tellurides have been prepared starting from AgN03 and re9. The method involves mixing together reactant solutions in the correct stoichiometry for the product with NH,OH(aq). The AgN03 can be used in aqueous solution, but Te must be dissolved in aqua regia. The resultant solution is then reduced using a mixture of N2H4.2HC1 and NH,OH, causing precipitation of the metal telluride in good yield. Similarly reaction of Se with Cu2+ or Ag+ solutions in NH3 yields products that approximate to Cu2Se and Ag2Se". Analogous reactions of Te with Cu2+solutions yield Cu2Te or CuTe depending on conditions. Reaction of Te with either AgCl or AgN03 in ammoniacal solution for prolonged periods precipitates Ag2Te. However, Te reduces AuCl solution to metallic Au irrespective of the reaction temperature. Whereas Se reduces Ag solutions when cold, it has no effect on Au solutions until almost boiling, at which point Au is precipitated. Selenides and tellurides of Hg and Cu are prepared by precipitation from solutions of selected metal salts in acidic solution". In the formation of HgTe, a solution of Te in aqua regia is added to Hg dissolved in H N 0 3 . The mixture is reduced by addition to a boiling solution of (NH4)2S03and acetic acid12. (E. M. PAGE) I. L. Karagiozov, E. Trifona, Cryst. Res. Techno/.,19, 447 (1984). 2. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 3. M. F. Banoch, P. Golebom, G. F. Hevenh, Acta Phys. Chem., Szeged, 4, 97 (1958). 4. E. Montignie, Ann. Pharm. Fr., I , 107 (1943); Chem. Abst., 40, 4307 (1946). 5. E. Montignie, Ann. Pharm. Fr., 4 , 251 (1946); Chem. Abst., 41, 6829 (1947). 6. L. Moser, K. Atynski, Monatsh. Chem., 45, 235 (1925). 7. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 8. W. Geilmann, W. Wrigge, Z. Anorg. Allg. Chem., 210, 378 (1933). 9. S. M. Kulifay, J . Am. Chem. Soc., 83, 4916 (1961). 10. R. D. Hall, V. Lenher, J . Am. Chem. Soc., 24, 918 (1902). 11. S. M. Kulifay, U. S. Patent 3026,175 (1962); Chem. Abst. 57, 267 (1962). 12. E. C. Parkman, Am. J . Sci., 2, 33, 328 (1862). 13. B. J. Aylett, in Comprehensice Inorganic Chemistry, Vol. 3, A. F. Trotman-Dickenson. ed., Pergamon Press, Oxford, 1973. p. 187. 3.7.4.2.2 Ternary Compounds
A general synthesis of Cu and Au chalcogenide halides in which M-Y bonds are formed (M = Cu: Au; Y = Se, Te) has been reported', and the syntheses have been reviewed2. Only sulfido halides are known for Ag whereas for Cu and Au there are reports of seleno- and tellurohalides only. Starting materials and conditions are listed in Table 11,3-10. Reaction occurs between the elemental chalcogen and binary group IB metal halide in the appropriate hydrohalic acid. The components are added to a silica ampule, which is sealed at liquid N2 temperature and allowed to warm slowly. Excessive pressures may develop, and a heavy face shield should be worn during this reaction.
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.3 By Reactions of Binary Acids of Selenium and Tellurium
35
TABLE1. TERXARY COMPOUNDS Product
Reactants
Media
Temperature ("C)
Time (days)"
Ref.
CuClSe, CuBrSe3 CuISe, CuClTe CuBrTe CuCITe, C u Br T e CuITe, AuClSe AuBrSe AuITe AuITe, AuBrTe, AuCITe,
CuCl + Se CuBr + Se CuI Se CuCl + Te CuBr + Te CuCl + Te CuBr + Te Cur Te Au + Se + C12 Au + Se + Br, Au + Te + I, Au + Te + HI Au + Te + HBr Au + Te + HC1
12 M HC1 9 MHBr 5 MHI 1 MHCI 1 MHBr 12 M HCI 9 MHBr 1MHI 12 MHC1 9 MHBr HI 10 M H I 9 MHBr HC 1
350-150 340-150 390-200 350-150 400- 150 350-150 400- 150 440- 150 200- 180 230 450-150 450-150 350-150 400-100
10 10 10 10 10 12 10 10 12 9 10 10 10 10
1, 3, 4 3, 4 3, 4 3, 4 3, 4 1, 3, 4 1, 3, 4 1, 3, 4 8, 9 8 5, 10 3 5, 6 7
,
+
+
"The general procedure involves heating the reaction mixture to the first temperature given and allowing the mixture to cool to the second temperature over the indicated number of days
The ampule is inserted in an autoclave, and a very high external pressure of C 0 2 applied to prevent explosion. The reaction mixture is then heated to the higher temperature quoted in Table 1 and allowed to cool to the lower temperature over the specified period of time'a3'4. Various Cu seleno- and t e l l ~ r o h a l i d e s and ' ~ ~ Au seleno- and t e l l ~ r o h a l i d e s ~have -~ been prepared this way. No ternary compounds were found in the systems Ag2Se-AgI and Ag2Te-AgI. (E. M. PAGE)
A. Rabenau, H. Rau, G. Rosenstein, Z. Anorg. Allg. Chem., 374, 43 (1970). D. A. Rice, Coord. Chem. Re@.,25, 219 (1978). A. Rabenau, H. Rau, Inorg. Synth., 14, 160 (1973). A. Rabenau, H. Rau, G. Rosenstein, Naturwisenchaften, 56, 137 (1969). A. Rabenau, H. Rau, G. Rosenstein, J . Less Common Met., 21, 395 (1970). A. Rabenau, H. Rau, G. Rosenstein, Angew. Chem., Int. Ed. Engl., 8, 145 (1969). A. Rabenau, H. Rau, at Third International Conference on Solid Compounds and Transition Elements, Oslo, Norway, June 1969. 8. A. Rabenau, H. Rau, G. Rosenstein, Monatsh. Chem., 102, 1425 (1971). 9. D. Motz, A. Rabenau, H. Wunderlich, J . Solid State Chem., 6, 583 (1973). 10. B. Reuter, K. Hardel, Z. Anorg. Allg. Chem., 340, 158 (1965). 1. 2. 3. 4. 5. 6. 7.
3.7.4.3 By Reactions of Binary Acids of Selenium and Tellurium and Their Derivatives by Reaction with Metal Compounds
Reaction of H2Se with aqueous group IIB metal divalent salt solutions provides a general route to group IIB metal selenides (Table l)'-'. Reaction between HzSe and aqueous ZnS04, buffered with ammonium acetate, yields cubic ZnSe. The ZnS04 solution should be added dropwise to a saturated solution
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.3 By Reactions of Binary Acids of Selenium and Tellurium
35
TABLE1. TERXARY COMPOUNDS Product
Reactants
Media
Temperature ("C)
Time (days)"
Ref.
CuClSe, CuBrSe3 CuISe, CuClTe CuBrTe CuCITe, C u Br T e CuITe, AuClSe AuBrSe AuITe AuITe, AuBrTe, AuCITe,
CuCl + Se CuBr + Se CuI Se CuCl + Te CuBr + Te CuCl + Te CuBr + Te Cur Te Au + Se + C12 Au + Se + Br, Au + Te + I, Au + Te + HI Au + Te + HBr Au + Te + HC1
12 M HC1 9 MHBr 5 MHI 1 MHCI 1 MHBr 12 M HCI 9 MHBr 1MHI 12 MHC1 9 MHBr HI 10 M H I 9 MHBr HC 1
350-150 340-150 390-200 350-150 400- 150 350-150 400- 150 440- 150 200- 180 230 450-150 450-150 350-150 400-100
10 10 10 10 10 12 10 10 12 9 10 10 10 10
1, 3, 4 3, 4 3, 4 3, 4 3, 4 1, 3, 4 1, 3, 4 1, 3, 4 8, 9 8 5, 10 3 5, 6 7
,
+
+
"The general procedure involves heating the reaction mixture to the first temperature given and allowing the mixture to cool to the second temperature over the indicated number of days
The ampule is inserted in an autoclave, and a very high external pressure of C 0 2 applied to prevent explosion. The reaction mixture is then heated to the higher temperature quoted in Table 1 and allowed to cool to the lower temperature over the specified period of time'a3'4. Various Cu seleno- and t e l l ~ r o h a l i d e s and ' ~ ~ Au seleno- and t e l l ~ r o h a l i d e s ~have -~ been prepared this way. No ternary compounds were found in the systems Ag2Se-AgI and Ag2Te-AgI. (E. M. PAGE)
A. Rabenau, H. Rau, G. Rosenstein, Z. Anorg. Allg. Chem., 374, 43 (1970). D. A. Rice, Coord. Chem. Re@.,25, 219 (1978). A. Rabenau, H. Rau, Inorg. Synth., 14, 160 (1973). A. Rabenau, H. Rau, G. Rosenstein, Naturwisenchaften, 56, 137 (1969). A. Rabenau, H. Rau, G. Rosenstein, J . Less Common Met., 21, 395 (1970). A. Rabenau, H. Rau, G. Rosenstein, Angew. Chem., Int. Ed. Engl., 8, 145 (1969). A. Rabenau, H. Rau, at Third International Conference on Solid Compounds and Transition Elements, Oslo, Norway, June 1969. 8. A. Rabenau, H. Rau, G. Rosenstein, Monatsh. Chem., 102, 1425 (1971). 9. D. Motz, A. Rabenau, H. Wunderlich, J . Solid State Chem., 6, 583 (1973). 10. B. Reuter, K. Hardel, Z. Anorg. Allg. Chem., 340, 158 (1965). 1. 2. 3. 4. 5. 6. 7.
3.7.4.3 By Reactions of Binary Acids of Selenium and Tellurium and Their Derivatives by Reaction with Metal Compounds
Reaction of H2Se with aqueous group IIB metal divalent salt solutions provides a general route to group IIB metal selenides (Table l)'-'. Reaction between HzSe and aqueous ZnS04, buffered with ammonium acetate, yields cubic ZnSe. The ZnS04 solution should be added dropwise to a saturated solution
36
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.3 By Reactions of Binary Acids of Selenium and Tellurium
TABLE1. PRODUCT OF REACTIONS WITH METALCOMPOUNDS Product ZnSe ZnTe ZnSe CdSe CdTe CdSe HgSe HgTe CuSe MY AgSe Ag,Te
Reactants
Ref.
ZnS04 + HzSe ZnS04 + H2Te ZnCl,(g) + H,Se Cd2+ + H,Se CdZt + H,Te CdS + H2Se HgC1, + H2Se HgCl, + H,Te C u t or Cuz+ + H,Se M Z t NazY or (NH4),Y (M=Zn, Cd, Hg, Cu; Y =Se, Te) Agt + H2Se Agt + HzTe
+
1, 2, 7 1 1 3, 4 3, 4 7 1, 5, 6 8 6 3, 9 5 5
of H2Se. Reaction is accelerated by passing through the solution a current of HZSe diluted with H Z or Nz. The resulting ZnSe precipitate is very fine and extremely air sensitive when moist. Centrifugation is often necessary to separate it from the solution, and then the dried precipitate is heated at 600°C for 2-4 h in a stream of H2 or H2Se to remove oxidation CdSe is obtained in an analogous manner starting with salts of Cd2+3,4.HgSe is formed from reaction between saturated aqueous H2Se and HgC12 solutions: HgClz
+ HZSe-
HgSe
+ 2HC1
(a)
The HgC12 is added dropwise to prevent precipitate contamination with the complex HgC12.2HgSe'.s*6. The reactions above can also be carried out with sodium or ammonium selenide as the selenium carrier: MClz + (NH4)2Se-
MSe
+ 2NH4Cl
(b)
Hexagonal ZnSe is obtained by treating ZnClz vapor with H2Se'. Heavy metal tellurides are prepared by HC1 treatment of an aqueous solution of a suitable salt such as the chloride, sulfate, or nitrate6. (E. M. PAGE)
1. G. Brauer, Handbook of Preparatise Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 2. R. Juza, A. Rabenau, G. Pascher, 2. Anorg. Allg. Chem., 285, 61 (1956). 3. D. M. Chizhikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 4. H. Uelsman, C. Faber, Ann. Chem. Phys., 10, 482 (1887). 5. B. J. Aylett, in Comprehensioe Inorganic Chemistry, Vol. 3, A. F. Trotman-Dickenson, ed., Pergamon Press, Oxford, 1973, p. 187. 6. L. Moser, K. Atynski, Monatsh. Chem., 45, 235 (1925). 7. M. F. Banoch, P. Golebom, G. F. Hevenh, Acta Phys. Chem., Szeged, 4 , 97 (1958). 8. A. Brukl, Monatsh. Chem., 45, 471 (1924). 9. D. M. Chizhikov, V. P. Shchastlivyi, Tellurium and Tellurides, Collets, London, 1970.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.5 Anions and Oxyanions of the Elements with Metal Compounds
37
3.7.4.4 By Reaction of Oxides of Selenium and Tellurium with Metal Compounds Selenium dioxide, S e 0 2 ,has been used to prepare selenides of group IIB metals (see Table 1)'-'. Both ZnSe and CdSe are obtained by heating the metal sulfide with Se0' at temperatures up to 800cC'-3. A study of the ZnS-SeO2 reaction showed that the main reaction forms ZnSe, and stops at 400-500°C. Simultaneously, a side reaction occurs in which ZnS is oxidized exothermically to ZnS04 and ZnO by SeO2. The ZnSe obtained from this reaction must be further purified to remove ZnO. TABLE1. S e 0 2 REACTIONS TO FORM GROUP IIA SELENIDES Product
ZnSe CdSe HgSe AgzTe
Metal Compound
Oxide
ZnS CdS HgC12/NaCN/NH,0H Ag2O
Se02 SeOz Se02/S02 Te02
Conditions
Aqueous solution
Ref. 1, 2 3 4 5
Mercury selenide has been reported from complex reaction between an aqueous mixture of Hg(I1) chloride and NaCN, made alkaline with NH40H, and SeO2. After filtration of the mixture, SO' is introduced whereupon HgSe is precipitated4:
-
+ 2NaCN + 8NH40H + SeO2 + 3so2 HgSe + 2NaCl+ 2NH4CN + 3(NH4)'S04 + 4H20
HgClz
(a) (E. M. PAGE)
1. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 2. L. Ya. Markovskii, R. N. Smirnova, Russ. J . Inorg. Chem., 5, 993 (1960). 3. L. Ya. Markovskii, R. N. Smirnova, Zh. Neorg. Khim., 6, 948 (1961). 4. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 5. E. Montignie, Bull. Soc. Chim. Fr., 13, 175 (1946).
3.7.4.5 By Reactions of the Anions and Oxyanions of the Elements with Metal Compounds
ZnSe is obtained by calcining the slurry obtained from reaction of ZnS with selenous acid, H2Se03.Reaction is complex but seems to proceed via initial formation of ZnSe03. This phase disappears at 400°C when ZnSe is produced','. Reaction between Zn(NH&SeO3, Cd(NH3)Se03, or Cu(NH&Se03 (3 < x < 6) with hydrazine at 80-85°C results in formation of the salt MSeNzH4 (M = Zn, Cd, Cu), which can be decomposed at 70-85°C with excess CH3COOH to yield MSe''3. The amine solution must contain free NH3. Small quantities of ethanoic acid must be added as a catalyst. Precipitates of the heavy metal selenides are filtered, washed, and dried in an inert atmosphere. This is the most widely used method for formation of CdSe. Heavy metal tellurides are also obtained this way4. Reaction of Zn2+ and C d Z + salts with selenosulfites provides another method for formation of MSe (M = Zn, Cd)'-*. Cd2+ + SeSOj-
+ H2O-
CdSe
+ 2H+ + Sol-
(a)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.5 Anions and Oxyanions of the Elements with Metal Compounds
37
3.7.4.4 By Reaction of Oxides of Selenium and Tellurium with Metal Compounds Selenium dioxide, S e 0 2 ,has been used to prepare selenides of group IIB metals (see Table 1)'-'. Both ZnSe and CdSe are obtained by heating the metal sulfide with Se0' at temperatures up to 800cC'-3. A study of the ZnS-SeO2 reaction showed that the main reaction forms ZnSe, and stops at 400-500°C. Simultaneously, a side reaction occurs in which ZnS is oxidized exothermically to ZnS04 and ZnO by SeO2. The ZnSe obtained from this reaction must be further purified to remove ZnO. TABLE1. S e 0 2 REACTIONS TO FORM GROUP IIA SELENIDES Product
ZnSe CdSe HgSe AgzTe
Metal Compound
Oxide
ZnS CdS HgC12/NaCN/NH,0H Ag2O
Se02 SeOz Se02/S02 Te02
Conditions
Aqueous solution
Ref. 1, 2 3 4 5
Mercury selenide has been reported from complex reaction between an aqueous mixture of Hg(I1) chloride and NaCN, made alkaline with NH40H, and SeO2. After filtration of the mixture, SO' is introduced whereupon HgSe is precipitated4:
-
+ 2NaCN + 8NH40H + SeO2 + 3so2 HgSe + 2NaCl+ 2NH4CN + 3(NH4)'S04 + 4H20
HgClz
(a) (E. M. PAGE)
1. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London, 1968. 2. L. Ya. Markovskii, R. N. Smirnova, Russ. J . Inorg. Chem., 5, 993 (1960). 3. L. Ya. Markovskii, R. N. Smirnova, Zh. Neorg. Khim., 6, 948 (1961). 4. G. Brauer, Handbook of Preparatice Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 5. E. Montignie, Bull. Soc. Chim. Fr., 13, 175 (1946).
3.7.4.5 By Reactions of the Anions and Oxyanions of the Elements with Metal Compounds
ZnSe is obtained by calcining the slurry obtained from reaction of ZnS with selenous acid, H2Se03.Reaction is complex but seems to proceed via initial formation of ZnSe03. This phase disappears at 400°C when ZnSe is produced','. Reaction between Zn(NH&SeO3, Cd(NH3)Se03, or Cu(NH&Se03 (3 < x < 6) with hydrazine at 80-85°C results in formation of the salt MSeNzH4 (M = Zn, Cd, Cu), which can be decomposed at 70-85°C with excess CH3COOH to yield MSe''3. The amine solution must contain free NH3. Small quantities of ethanoic acid must be added as a catalyst. Precipitates of the heavy metal selenides are filtered, washed, and dried in an inert atmosphere. This is the most widely used method for formation of CdSe. Heavy metal tellurides are also obtained this way4. Reaction of Zn2+ and C d Z + salts with selenosulfites provides another method for formation of MSe (M = Zn, Cd)'-*. Cd2+ + SeSOj-
+ H2O-
CdSe
+ 2H+ + Sol-
(a)
38
3.7 Formation of the Group VIB-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.5 Anions and Oxyanions of the Elements with Metal Compounds
TABLE1. FORMATION OF SELENITESAND SELENATES
Product MSe (M=Zn, Cd) ZnSe CdSe MSeO, MTeO, (M =Zn, Cu) ZnYO, (Y =Se, Te) CuSeO, Ag~Se04 Ag2Te04 A U 2 (SeO,), AUZ(Se0&
Compound
Anion
MS ZnSO, Cd2+ M2 M2 Zn2 Cu(OH)z AgzC03 Ag2CO3 Au Au(OHL
H2Se0, (Na,SO,),Se SeS0,2H2Se0, H,TeO, HZYO, H,SeO, H2Se0, H,TeO, H,SeO, H,SeO,
+
+
Conditions
Ref.
750-850'C Acid solution
1, 2 7, 8 7 9, 10 12 9, 10 11 13 13 12 11
Aqueous solution Aqueous solution Aqueous solution 154°C for 13 h
However, CdS04, CdS, and Se are all precipitated from solution along with CdSe and must be removed by warming with 0.5 M HC1. This method is useful; it provides good yields of ZnSe and CdSe and eliminates the need for use of toxic HzSe. Many group IB and IIB metal salts react with selenous acid, H2Se03, and selenic acid, HzSe04, or their sodium salts forming selenites and selenates (Table ZnSe03, ZnSe04, ZnTe03 and ZnTe0, all form from metathetical reactions or, as in the case of ZnSe04, by dissolving ZnO in selenic a ~ i d ~ ~ ' ~ . Freshly precipitated Cu(0H)z can be dissolved in the calculated amount of selenic acid, HZSe04, yielding double salts of formula MZCu(Se04)2 6 H z 0 in the presence of alkali metals". Gold is dissolved by selenic acid, giving Au2(Se04)3. Reaction involves heating Au metal and 98% selenic acid at 154°C for 13 h, after which golden yellow crystals of Auz(Se04)3 form". Gold selenite, Auz(SeO&, is obtained from gold hydroxide and selenous acid14: l)13237-13.
2Au(OH)3
+ 3H~Se03-
A u ~ ( S e 0 3+ ) ~6 H z 0
(b) (E. M. PAGE)
1. D. M. Chizikov, V. P. Shchastlivyi, Selenium and Selenides, Collets, London (1968). 2. G. Brauer, Handbook of Preparatine Inorganic Chemistry, Vol. 2, Academic Press, New York, 1965. 3. W. Bonziag, U. S. Patent 2,921,834 (1960). 4. D. M. Chizhikov, V. P. Shchastlivyi, Tellurium and Tellurides, Collets, London, 1970. 5. B. Ratke, J . Prakt. Chem., 92, 141 (1864). 6. E. Pitzer, N. Gordon, Ind. Eng. Chem. Anal. Ed., 10, 68 (1938). 7. I. P. Kalinkin, L. A. Sergeeva, V. B. Alekseevskii, L. P. Strakhov, Fiz. Tcerd. Tela, 5 , 124 (1963). 8. N. E. Gordon, E. C. Pitzer, U. S. Patent 2,176,495 (1939). 9. A. Schleede, J. Glassner, German Patent 699,320 (1938). 10. L. Ya. Markovskii, G. F. Pron, Zh. Neorg. Khim., 13, 2640 (1968). 11. A. E. H. Tutton, Proc. R. Soc., A98, 67 (1921). 12. W. E. Caldwell, L. P. Eddy, J . Am. Chem. Soc., 71, 2247 (1949). 13. B. J. Aylett, in Comprehensive Inorganic Chemistry, Vol. 3, A. F. Trotman-Dickenson, ed., Pergamon Press, Oxford, 1973, p. 187. 14. H. Schmidtke, D. Garthoff, Helc. Chirn. Acta, 50, 1631 (1967).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 39 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.1 By Reaction with the Metals 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.1 By Reaction with the Metals
3.7.4.6.1.1 Chemically Driven Reactions. The low reactivity of most group IB and IIB elements restricts direct reaction between the metal and donor ligands containing Se and Te. Mercury is the exception; it is particularly susceptible to oxidative addition by dichalcogenides (Table l)1-6.This route is convenient for syntheses of complexes with sterically undemanding ligands but becomes less facile as the Hg-chalcogen bond strength decreases in the sequence S > Se > Te. The resulting H g complexes show great structural diversity. The small alkylthiolato complexes Hg(SR), (R = Me, Et) exist as essentially monomeric linear molecules in the solid state, whereas related selenolates form infinite polymeric lattices. The complexes Hg(SeR), (R = Me, Et) are obtained by prolonged reaction between Hg and the appropriate dialkyl diselenide in either pyridine or CHCl3 X-ray studies show the methyl adduct to be polymeric, with chains of Se atoms extending along the b axis and bridging the pseudotetrahedrally coordinated Hg atoms. Similarly, the bistellurolato complex Hg(TeMe3C6H2)2forms by addition of Hg metal to a stirred solution of ArzTez in toluene at RT. A pale yellow precipitate identified as Hg(TeMe3C6H2),is obtained after 24 h2. Trifluoromethylselenyl chloride, CF,SeCI, reacts rapidly with Hg yielding Hg(SeCF,),. The complex can also be obtained from reaction between Hg and (CF3)2Se2'. An interesting reaction has been reported between Hg and the Ir diseleno complex [Ir(Se2)(dmpe)z]C14.Treatment of the complex with Hg in MeCN results in mercuration yielding the tetramer [(dmpe)21r(p-Se),Hg],C14 in which Hg has inserted into a Se-Se group and also bridges to an adjacent Sez group. The reaction corresponds to oxidative addition across a Se-Se bond. The products formed in reactions between Hg and complexes of general formula [M-(Se)2(L-L)2]C1 depend on the nature of the metal M and basicity of the ditertiary phosphine (L-L). Generally, if M = Rh and L-L = dmpe or M = Ir and L-L = dppe, H g reacts by stripping away Se as HgSe:
'.
[M(Se),(L-L),]+
+ 2Hg
-
[M-(L-L),]+
+ 2HgSe
(a)
TABLE1. COMPLEXES IN WHICH A GROUP IIB METALBONDSTO SELENIUM OR TELLURIUM FORMED BY REACTIONOF THE GROUP IIB METAL WITH LIGANDS CONTAINING Se OR Te
Complex Hg(SeMe)2 Hg(SeEt)Z Hg(TW2 (Ar = 2,4,6-Me3C6H2) Hg(SeCF3)* Hg(SeCF3)2
(p-EtOC6H4Te),Hg ZnSe,(N-MeIm), (Im = imidazole)
Reaction Hg + Me2Se2
Hg
+ EtzSe,
Hg + Ar,Te,
Conditions Pyridine for 2 days CHC13 for 1 day Toluene, stir for 24 h
2
C6H6 for 48 h 100°C for 18 h
3 3 6 5
Hg + F3CSeC1
+ (CF3)2Se2
Hg + (p-EtOC6H4)2TeZ Zn + Se + (N-MeIm)
Ref. 1
1
40 3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds ~
~~
The solid phase reaction of Zn dust in hot N-methylimidazole (N-MeIm) with Se for 18 h yields the complex ZnSe4(N-MeIm)2,which possesses tetrahedrally coordinated Zn and nonplanar ZnSe4 rings5. (E. M. PAGE)
1. 2. 3. 4. 5. 6.
A. P. Arnold, A. J. Canty, Inorg. Chim. Acta, 55, 171 (1981). M. Bochmann, K. J. Webb, Inorg. Synth., 31, 24 (1997). J. W. Dale, H. J. Emeleus, R. N. Hazeldine, J . Chem. Soc., 2939 (1958). A. P. Ginsberg, C. R. Sprinkle, J . Am. Chem. SOC., 107, 5550 (1985). S. Dev, E. Ramli, T. B. Rauchfuss, C. L. Stern, J. Am. Chem. Soc., 112, 6385 (1990). N. S. Dance and C. H. W. Jones, J . Organomet. Chem., 152, 175 (1998).
3.7.4.6.1.2 Electrochemically Driven Reactions. Novel electrochemical methods can be employed to enhance reactivity of group IB and IIB metals by making them the anode in electrooxidation reactions. Reactions yielding M(SePh), (M = Zn, Cd) and MSePh (M = Cu, Ag) are carried out by dissolving PhzSez in toluene with MeCN and electrolyzing the solution using the appropriate group I or IIB metal as the anode'. Addition of 1,lO-phenanthroline or Ph3P to the solutions forms ligated complexes Table 1). TABLE1. COMPLEXES IN WHICH A GROUPIB OR IIB METALTO SELENIUM BONDIS FORMED BY ELECTROCHEMICAL REACTION BETWEEN THE METAL AND THE $2-CONTAINING LIGAND Product
Metal Anode
Reactants
M(SePh), (M = Zn, Cd) MSePh (M = CU, Ag) Cd(SePh), . 2 phenanthroline CuSePh' phenanthroline CuSePh. 1.5Ph3P
Zn, Cd
Ph,Se2
Cu, Ag
Ph2Se2
Cd
cu
Ph&, 1,lO-phenanthroline Ph2Se2, 1,lO-phenanthroline Ph2Se2,Ph3P
Ph,PCu(p-SePh), Cu(PPh3), MeCN
cu
Ph,Se2, Ph3P
cu
Solvent
Ref.
Toluene, CHC13, Et4NC104 Toluene, CHC13, Et4NC104 Toluene, CHC13, Et4NC104 Toluene, CHCI,, Et4NC104 Toluene, CHCl,, Et4NC104 Toluene, MeCN
1 1
1 1
1 2
Analogously, the p-Se bridged dimer Ph,PCu(p-SePh),(PPh& MeCN forms by electrooxidation of a Cu anode in a solution of PhzSez in MeCN-toluene'. (E. M. PAGE)
1. R. Kumar, D. G. Tuck, Can. J . Chem., 67, 127 (1989). 2. J. Kampf, R. Kumar, J. P. Oliver, Inorg. Chem., 31, 3626 (1992). 3.7.4.6.2 By Reactions with Metal Compounds
Reactions of group IB and IIB metal compounds with ligands containing Se and Te which form the metal-chalcogen bond are of considerable recent interest (see 3.7.4.7). Research in this area had been limited because of difficulties in the preparation and
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
40 3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds ~
~~
The solid phase reaction of Zn dust in hot N-methylimidazole (N-MeIm) with Se for 18 h yields the complex ZnSe4(N-MeIm)2,which possesses tetrahedrally coordinated Zn and nonplanar ZnSe4 rings5. (E. M. PAGE)
1. 2. 3. 4. 5. 6.
A. P. Arnold, A. J. Canty, Inorg. Chim. Acta, 55, 171 (1981). M. Bochmann, K. J. Webb, Inorg. Synth., 31, 24 (1997). J. W. Dale, H. J. Emeleus, R. N. Hazeldine, J . Chem. Soc., 2939 (1958). A. P. Ginsberg, C. R. Sprinkle, J . Am. Chem. SOC., 107, 5550 (1985). S. Dev, E. Ramli, T. B. Rauchfuss, C. L. Stern, J. Am. Chem. Soc., 112, 6385 (1990). N. S. Dance and C. H. W. Jones, J . Organomet. Chem., 152, 175 (1998).
3.7.4.6.1.2 Electrochemically Driven Reactions. Novel electrochemical methods can be employed to enhance reactivity of group IB and IIB metals by making them the anode in electrooxidation reactions. Reactions yielding M(SePh), (M = Zn, Cd) and MSePh (M = Cu, Ag) are carried out by dissolving PhzSez in toluene with MeCN and electrolyzing the solution using the appropriate group I or IIB metal as the anode'. Addition of 1,lO-phenanthroline or Ph3P to the solutions forms ligated complexes Table 1). TABLE1. COMPLEXES IN WHICH A GROUPIB OR IIB METALTO SELENIUM BONDIS FORMED BY ELECTROCHEMICAL REACTION BETWEEN THE METAL AND THE $2-CONTAINING LIGAND Product
Metal Anode
Reactants
M(SePh), (M = Zn, Cd) MSePh (M = CU, Ag) Cd(SePh), . 2 phenanthroline CuSePh' phenanthroline CuSePh. 1.5Ph3P
Zn, Cd
Ph,Se2
Cu, Ag
Ph2Se2
Cd
cu
Ph&, 1,lO-phenanthroline Ph2Se2, 1,lO-phenanthroline Ph2Se2,Ph3P
Ph,PCu(p-SePh), Cu(PPh3), MeCN
cu
Ph,Se2, Ph3P
cu
Solvent
Ref.
Toluene, CHC13, Et4NC104 Toluene, CHC13, Et4NC104 Toluene, CHC13, Et4NC104 Toluene, CHCI,, Et4NC104 Toluene, CHCl,, Et4NC104 Toluene, MeCN
1 1
1 1
1 2
Analogously, the p-Se bridged dimer Ph,PCu(p-SePh),(PPh& MeCN forms by electrooxidation of a Cu anode in a solution of PhzSez in MeCN-toluene'. (E. M. PAGE)
1. R. Kumar, D. G. Tuck, Can. J . Chem., 67, 127 (1989). 2. J. Kampf, R. Kumar, J. P. Oliver, Inorg. Chem., 31, 3626 (1992). 3.7.4.6.2 By Reactions with Metal Compounds
Reactions of group IB and IIB metal compounds with ligands containing Se and Te which form the metal-chalcogen bond are of considerable recent interest (see 3.7.4.7). Research in this area had been limited because of difficulties in the preparation and
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
40 3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds ~
~~
The solid phase reaction of Zn dust in hot N-methylimidazole (N-MeIm) with Se for 18 h yields the complex ZnSe4(N-MeIm)2,which possesses tetrahedrally coordinated Zn and nonplanar ZnSe4 rings5. (E. M. PAGE)
1. 2. 3. 4. 5. 6.
A. P. Arnold, A. J. Canty, Inorg. Chim. Acta, 55, 171 (1981). M. Bochmann, K. J. Webb, Inorg. Synth., 31, 24 (1997). J. W. Dale, H. J. Emeleus, R. N. Hazeldine, J . Chem. Soc., 2939 (1958). A. P. Ginsberg, C. R. Sprinkle, J . Am. Chem. SOC., 107, 5550 (1985). S. Dev, E. Ramli, T. B. Rauchfuss, C. L. Stern, J. Am. Chem. Soc., 112, 6385 (1990). N. S. Dance and C. H. W. Jones, J . Organomet. Chem., 152, 175 (1998).
3.7.4.6.1.2 Electrochemically Driven Reactions. Novel electrochemical methods can be employed to enhance reactivity of group IB and IIB metals by making them the anode in electrooxidation reactions. Reactions yielding M(SePh), (M = Zn, Cd) and MSePh (M = Cu, Ag) are carried out by dissolving PhzSez in toluene with MeCN and electrolyzing the solution using the appropriate group I or IIB metal as the anode'. Addition of 1,lO-phenanthroline or Ph3P to the solutions forms ligated complexes Table 1). TABLE1. COMPLEXES IN WHICH A GROUPIB OR IIB METALTO SELENIUM BONDIS FORMED BY ELECTROCHEMICAL REACTION BETWEEN THE METAL AND THE $2-CONTAINING LIGAND Product
Metal Anode
Reactants
M(SePh), (M = Zn, Cd) MSePh (M = CU, Ag) Cd(SePh), . 2 phenanthroline CuSePh' phenanthroline CuSePh. 1.5Ph3P
Zn, Cd
Ph,Se2
Cu, Ag
Ph2Se2
Cd
cu
Ph&, 1,lO-phenanthroline Ph2Se2, 1,lO-phenanthroline Ph2Se2,Ph3P
Ph,PCu(p-SePh), Cu(PPh3), MeCN
cu
Ph,Se2, Ph3P
cu
Solvent
Ref.
Toluene, CHC13, Et4NC104 Toluene, CHC13, Et4NC104 Toluene, CHC13, Et4NC104 Toluene, CHCI,, Et4NC104 Toluene, CHCl,, Et4NC104 Toluene, MeCN
1 1
1 1
1 2
Analogously, the p-Se bridged dimer Ph,PCu(p-SePh),(PPh& MeCN forms by electrooxidation of a Cu anode in a solution of PhzSez in MeCN-toluene'. (E. M. PAGE)
1. R. Kumar, D. G. Tuck, Can. J . Chem., 67, 127 (1989). 2. J. Kampf, R. Kumar, J. P. Oliver, Inorg. Chem., 31, 3626 (1992). 3.7.4.6.2 By Reactions with Metal Compounds
Reactions of group IB and IIB metal compounds with ligands containing Se and Te which form the metal-chalcogen bond are of considerable recent interest (see 3.7.4.7). Research in this area had been limited because of difficulties in the preparation and
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 41 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.1 Alkali Metal Selenides, Polyselenides, Tellurides, and Polytellurides
handling of organo Se and Te derivatives, which are unstable, toxic, and foul smelling'. Group IIB selenolate and tellurolate derivatives are among the oldest and most common metal complexes with these ligands. At present they find important uses as single-source precursors to group 11-VI semiconductors. Recently, interest in group IB and IIB Seand Te-containing complexes increased markedly for a variety of reasons: they might have possible uses in formation of electronic materials and Au chalcogenates are beginning to find applications in the sensitization of photographic materials, in electron microscopy, and in the treatment of arthritis and cancer. A recent review of metal complexes with selenolate and tellurolate ligands emphasizes particularly some of the more novel developments in the field2. Synthetic reagents and routes to the complexes are surveyed, and main group and transition metal derivatives and their structures described in detail. (E. M. PAGE)
1. H. J. Gysling, in The Chemistry of Organic Selenium and Tellurium Compounds, Vol. 1, S. Patai, Z. Rappoport, eds., Wiley, New York, 1986, p. 679. 2. J. Arnold, Prog. Inorg. Chem., 43, 353 (1995).
3.7.4.6.2.1 Reaction with Alkali Metal Selenides, Polyselenides, Tellurides, and Polytellurides. Group IB and IIB selenides and tellurides are readily prepared by reaction of a metal salt with an alkali metal polychalcogenide of general formula A2E, (A = alkali metal; E = Se, Te; y = 1-6). These complexes easily form when the elements are melted in a quartz tube or when the group IA metal is dissolved in liquid NH3, followed by reduction of the chalcogen and removal of NH3. The metal cations are metathesized with large organic counterions to give salts like [(Ph),P], [Te4] and [ ( B u ) ~ N[Se5]. ] ~ Such species are highly crystalline and structurally well characterized, although the nature of the polychalcogenide in solution is not well understood'. In a typical reaction to form the metal-chalcogenide bond, the polychalcogenide reacts with the metal salt in a polar solvent such as DMF'. Reaction is driven by the nucleophilicity of the polychalcogenide anion. Formation of a range of heavy metal selenides and tellurides from polychalcogenides is described in articles that discuss the polychalcogenide ions and the synthesis, structure, and reactivity the complexes A first report of this route involved formation of MTe (M = Zn, Cd, Cu), CuzTe3, and AgzTe by reaction of the metal acetate with sodium telluride acidified with ethanoic acid, to prevent precipitation of the metal hydroxide5. The metal telluride precipitates. Examples of complexes prepared this way are listed in Table 15-14. Many products arise when a solution of cation is added to the reaction mixture of Na2Se, and AgN03 in DMF6. The [WSe,]'- ion can also be used as a source of Se in reactions to give complexes with bonds between Se and a group IB metal7. The polytelluride ligand provides a useful synthetic route to Ag(1) and Cu(1)-Te complexes'. The [AgTe4] - ions formed consist of five-membered AgTe, rings connected by bridging Te atoms such that each Ag atom is coordinated by three [Te4I2- ligands. The [M2Te1J4- ion forms from reaction of Na2Te3 with CuCl or AgN03 in D M F in the presence of PPh4Brg.In the Ag complex, each metal atom is linked by a chain of four Te atoms and ligated bidentately by a ring of four Te atoms so that each Ag atom is again tri-coordinated. Formation of (p-Te,) bridged complexes is effected using a mixture of LizTe and Te powder, which provides a polytelluride solution in DMF".
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 41 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.1 Alkali Metal Selenides, Polyselenides, Tellurides, and Polytellurides
handling of organo Se and Te derivatives, which are unstable, toxic, and foul smelling'. Group IIB selenolate and tellurolate derivatives are among the oldest and most common metal complexes with these ligands. At present they find important uses as single-source precursors to group 11-VI semiconductors. Recently, interest in group IB and IIB Seand Te-containing complexes increased markedly for a variety of reasons: they might have possible uses in formation of electronic materials and Au chalcogenates are beginning to find applications in the sensitization of photographic materials, in electron microscopy, and in the treatment of arthritis and cancer. A recent review of metal complexes with selenolate and tellurolate ligands emphasizes particularly some of the more novel developments in the field2. Synthetic reagents and routes to the complexes are surveyed, and main group and transition metal derivatives and their structures described in detail. (E. M. PAGE)
1. H. J. Gysling, in The Chemistry of Organic Selenium and Tellurium Compounds, Vol. 1, S. Patai, Z. Rappoport, eds., Wiley, New York, 1986, p. 679. 2. J. Arnold, Prog. Inorg. Chem., 43, 353 (1995).
3.7.4.6.2.1 Reaction with Alkali Metal Selenides, Polyselenides, Tellurides, and Polytellurides. Group IB and IIB selenides and tellurides are readily prepared by reaction of a metal salt with an alkali metal polychalcogenide of general formula A2E, (A = alkali metal; E = Se, Te; y = 1-6). These complexes easily form when the elements are melted in a quartz tube or when the group IA metal is dissolved in liquid NH3, followed by reduction of the chalcogen and removal of NH3. The metal cations are metathesized with large organic counterions to give salts like [(Ph),P], [Te4] and [ ( B u ) ~ N[Se5]. ] ~ Such species are highly crystalline and structurally well characterized, although the nature of the polychalcogenide in solution is not well understood'. In a typical reaction to form the metal-chalcogenide bond, the polychalcogenide reacts with the metal salt in a polar solvent such as DMF'. Reaction is driven by the nucleophilicity of the polychalcogenide anion. Formation of a range of heavy metal selenides and tellurides from polychalcogenides is described in articles that discuss the polychalcogenide ions and the synthesis, structure, and reactivity the complexes A first report of this route involved formation of MTe (M = Zn, Cd, Cu), CuzTe3, and AgzTe by reaction of the metal acetate with sodium telluride acidified with ethanoic acid, to prevent precipitation of the metal hydroxide5. The metal telluride precipitates. Examples of complexes prepared this way are listed in Table 15-14. Many products arise when a solution of cation is added to the reaction mixture of Na2Se, and AgN03 in DMF6. The [WSe,]'- ion can also be used as a source of Se in reactions to give complexes with bonds between Se and a group IB metal7. The polytelluride ligand provides a useful synthetic route to Ag(1) and Cu(1)-Te complexes'. The [AgTe4] - ions formed consist of five-membered AgTe, rings connected by bridging Te atoms such that each Ag atom is coordinated by three [Te4I2- ligands. The [M2Te1J4- ion forms from reaction of Na2Te3 with CuCl or AgN03 in D M F in the presence of PPh4Brg.In the Ag complex, each metal atom is linked by a chain of four Te atoms and ligated bidentately by a ring of four Te atoms so that each Ag atom is again tri-coordinated. Formation of (p-Te,) bridged complexes is effected using a mixture of LizTe and Te powder, which provides a polytelluride solution in DMF".
42 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.1 Alkali Metal Selenides, Polyselenides,Tellurides, and Polytellurides TABLE1. COMPLEXES FORMED FROM REACTION BETWEEN GROUP IB AND IIB METAL COMPOUNDS WITH ALKALI METALCHALCOGENIDES AND POLYCHALCOGENIDES Product
Reactants
+ +
Conditions
M(MeCOO), Na2Te Cu(MeCOO), + Na4Te, Ag(MeCO0) NazTe AgN0, Na2Se, Ph4PCI (1:2:2) AgN03 + NazSe, Me4NC1 (1 : 2 : 2) AgNO, Na2Se, Et4NCI (1:2:2) AgN03 Na2Se, Pr4NC1 (1:2 :2) AuCN (Na2Sez + Ph4PC1) (1 : 1) AuCN (K2Sez + Ph4PC1) (1:2) AuCN Na2Se3 + [(Ph,P),N]CI (1:2:2) M' in excess PMe2Ph + [NPr],[WSe,] (2: 1) (Ph3P),CuC1 + K2Te4+ Me4NC1 (1 : 1 : 1) AgBF4 + K,Te4 + Me4NC1 (1 : 1 : 1) AgNO, or CuCl + Na2Te, + Ph4PBr (CuC1 + PEt,) in T H F + [Li,Te + Te powder (1: 3)] in D M F PEt3) in ([Ag(Me,P)I], THF + [LizTe + Te powder (1 : 3)] in D M F AuCN + Na2Se + Et4NC1 Zn2+ + PhSe- + Se CdZ' PhSe- NazE
+
+ + + +
+ + + + +
+
+
+
Ref.
5 5
D M F for 10 rnin
5 6
D M F for 4 h
6
D M F for 10 rnin
6
D M F for 10 rnin
6
D M F for 1 h
14
DMF
14
DMF
14
MeCN for 30 rnin at RT
7
D M F for 30 rnin
8
D M F for 30 min
8
DMF
9
Warm for 1 h
10
Stir for 30 rnin
10
MeOH MeCN
11 12 13
Various cluster metal chalcogenide anions are obtained by reaction of a group IB or IIB metal salt with the polychalcogenide ion, often present as an alkyl or phenyl chalcogenide' 3. Some such syntheses require the presence of elemental chalcogen. (E. M. PAGE) 1. 2. 3. 4.
J. W. Kolis, Coord. Chem. Rev., 105, 195 (1990). M. G. Kanatzidis, S.-P. Huang, J . Am. Chem. SOC., I l l , 760 (1989). M. A. Ansari, J. A. Ibers, Coord. Chem. Reu., 100, 223 (1990). M. G. Kanatzidis, Comm. Inorg. Chem., 10, 161 (1990).
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 43 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.2 Reaction with Organochalcogenides C. A. Tibhals, J . Am. Chem. Soc., 83, 4916 (1961). S. P. Huang, M. G. Kanatzidis, lnorg. Chem., 30, 1455 (1991). C. C. Christuk, M. A. Ansari, J. A. Ihers, lnorg. Chem., 31, 4365 (1992). K.-W. Kim, M. G. Kanatzidis, J . Am. Chem. Soc., 115, 5871 (1993). D. Fenske, B. Schreiner, K. Dehnicke, Z. Anorg. Allg. Chem., 619, 253 (1993). M. A. Ansari, J. C. Bollinger, J. A. Ibers, lnorg. Chem., 32, 1746 (1993). S.-P. Huang, M. G. Kanatzidis, Angew. Chem., Int. Ed. Engl., 31, 787 (1992). I. G. Dance, A. Choy, M. L. Scudder, J . Am. Chem. SOC.,106, 6285 (1984). G. S. H. Lee, K. J. Fisher, D. C. Craig, M. L. Scudder, I. G. Dance, J . Am. Chem. Soc., 112,6435 (1990). 14. S.-P. Huang and M. G. Kanatzidis, lnorg. Chem., 30, 3572 (1991).
5. 6. 7. 8. 9. 10. 11. 12. 13.
3.7.4.6.2.2 Reaction with Organochalcogenides. An important route to bonds of group IB and IIB metals to Se or Te involves reaction of metal salts with an organoselenide or telluride (Table l)1-7.These ligands are readily obtained from the group IA metal chalcogenide by a metathetic reaction with an organic counterion. Some complexes whose syntheses directly from the metal were discussed in 3.7.4.6.1 can be prepared by these reactions. The largely organic nature of the complexes renders them readily crystallizable and fairly volatile; thus they have potential use as single molecule precursors in metal-organic chemical vapor deposition (MOCVD: 3.7.4.7). TABLE1. COMPLEXES FORMED FROMREACTION BETWEEN THE GROUPIB IIB METALCOMPOUND WITH AN ORGAiYOCHALCOGENIDE ~~
~
Complex R,Te,CuX (R = Et, n-Bu, n-C5HI1; X = C1, Br) RTeCu (R = Et, n-Bu, n-C5Hl1, Ph) CAg,(Ph,Te2)41 [AsF,] CAu(CH2)zP(Ph)zl(Ph12Se2 Hg(SeAr”), (Ar” = 2 , 4 , 6 - ( B ~ - t ) ~ C ~ H , ) MeHgSeBu-t (TeW2Hgx~ X = C1, Br, I (TePh21zHgI2 Me,TeI,HgBr, (p-EtOC,H,),TeHgX,
OR
Reaction
*.
CuX in MeCN
+ R,Te,
Conditions
Ref.
Stir at RT for 10 min in Et,O
1
+
CuCl in EtOH R2Te2+ NaBH,/NaOH Ag[AsF,] Ph2Te, CAu(CH,)2P(Ph)21, + (Ph)2Se2 HgC1, + Ar”SeLi (1 : 2)
1
+
Liquid SO2 THF T H F at RTfor 2h (MeHgOH + NaOH) + (Bu-t)Se MeOH HgX, TePh, EtOH
+ HgI, + excess TePh, Me,TeI, + HgBr,
(p-EtOC6H,),Te2
+ HgX,
EtOH EtOH
2 3 4 5 6
6 7
I
(E. M. PAGE)
1. 2. 3. 4. 5. 6. 7.
I. Davies, W. R. McWhinnie, N. S. Dance, C. H. W. Jones, lnorg. Chim. Acta, 29, L217 (1978). P. C. Srivastava, Indian J . Chem., Sect. A, 29, 75 (1990). L. C. Porter, J. P. Fackler, Acta Crystallogr., Sect. 43, 29 (1987). M. Bochmann, K. J. Webb, Inorg. Synth., 31, 24, (1997). J. W. Dale, H. J. Emeleus, R. N. Hazeldine, J . Chem. SOC.,2939 (1958). F. W. B. Einstein, C. H. W. Jones, R. D. Sharma, Inorg. Chem., 22, 3924 (1983). N. S. Dance, C. H. W. Jones, J . Organomet. Chem., 152, 175 (1978).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 43 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.2 Reaction with Organochalcogenides C. A. Tibhals, J . Am. Chem. Soc., 83, 4916 (1961). S. P. Huang, M. G. Kanatzidis, lnorg. Chem., 30, 1455 (1991). C. C. Christuk, M. A. Ansari, J. A. Ihers, lnorg. Chem., 31, 4365 (1992). K.-W. Kim, M. G. Kanatzidis, J . Am. Chem. Soc., 115, 5871 (1993). D. Fenske, B. Schreiner, K. Dehnicke, Z. Anorg. Allg. Chem., 619, 253 (1993). M. A. Ansari, J. C. Bollinger, J. A. Ibers, lnorg. Chem., 32, 1746 (1993). S.-P. Huang, M. G. Kanatzidis, Angew. Chem., Int. Ed. Engl., 31, 787 (1992). I. G. Dance, A. Choy, M. L. Scudder, J . Am. Chem. SOC.,106, 6285 (1984). G. S. H. Lee, K. J. Fisher, D. C. Craig, M. L. Scudder, I. G. Dance, J . Am. Chem. Soc., 112,6435 (1990). 14. S.-P. Huang and M. G. Kanatzidis, lnorg. Chem., 30, 3572 (1991).
5. 6. 7. 8. 9. 10. 11. 12. 13.
3.7.4.6.2.2 Reaction with Organochalcogenides. An important route to bonds of group IB and IIB metals to Se or Te involves reaction of metal salts with an organoselenide or telluride (Table l)1-7.These ligands are readily obtained from the group IA metal chalcogenide by a metathetic reaction with an organic counterion. Some complexes whose syntheses directly from the metal were discussed in 3.7.4.6.1 can be prepared by these reactions. The largely organic nature of the complexes renders them readily crystallizable and fairly volatile; thus they have potential use as single molecule precursors in metal-organic chemical vapor deposition (MOCVD: 3.7.4.7). TABLE1. COMPLEXES FORMED FROMREACTION BETWEEN THE GROUPIB IIB METALCOMPOUND WITH AN ORGAiYOCHALCOGENIDE ~~
~
Complex R,Te,CuX (R = Et, n-Bu, n-C5HI1; X = C1, Br) RTeCu (R = Et, n-Bu, n-C5Hl1, Ph) CAg,(Ph,Te2)41 [AsF,] CAu(CH2)zP(Ph)zl(Ph12Se2 Hg(SeAr”), (Ar” = 2 , 4 , 6 - ( B ~ - t ) ~ C ~ H , ) MeHgSeBu-t (TeW2Hgx~ X = C1, Br, I (TePh21zHgI2 Me,TeI,HgBr, (p-EtOC,H,),TeHgX,
OR
Reaction
*.
CuX in MeCN
+ R,Te,
Conditions
Ref.
Stir at RT for 10 min in Et,O
1
+
CuCl in EtOH R2Te2+ NaBH,/NaOH Ag[AsF,] Ph2Te, CAu(CH,)2P(Ph)21, + (Ph)2Se2 HgC1, + Ar”SeLi (1 : 2)
1
+
Liquid SO2 THF T H F at RTfor 2h (MeHgOH + NaOH) + (Bu-t)Se MeOH HgX, TePh, EtOH
+ HgI, + excess TePh, Me,TeI, + HgBr,
(p-EtOC6H,),Te2
+ HgX,
EtOH EtOH
2 3 4 5 6
6 7
I
(E. M. PAGE)
1. 2. 3. 4. 5. 6. 7.
I. Davies, W. R. McWhinnie, N. S. Dance, C. H. W. Jones, lnorg. Chim. Acta, 29, L217 (1978). P. C. Srivastava, Indian J . Chem., Sect. A, 29, 75 (1990). L. C. Porter, J. P. Fackler, Acta Crystallogr., Sect. 43, 29 (1987). M. Bochmann, K. J. Webb, Inorg. Synth., 31, 24, (1997). J. W. Dale, H. J. Emeleus, R. N. Hazeldine, J . Chem. SOC.,2939 (1958). F. W. B. Einstein, C. H. W. Jones, R. D. Sharma, Inorg. Chem., 22, 3924 (1983). N. S. Dance, C. H. W. Jones, J . Organomet. Chem., 152, 175 (1978).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
44 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.3 Reaction with Organoselenols and Tellurols 3.7.4.6.2.3 Reaction with Organoselenols and Tellurols. Formation of metal chalcogenato complexes from the metal halide (or acetate, nitrate, etc.) is not always suitable for introduction of bulky ligands that cause complexes to undergo thermal decomposition to the metal chalcogenide. Another synthetic route involves protolysis of metal bis(trimethylsily1)amides in nonpolar solvents by arene selenols and tellurols (Table l)1-6. These reactions generally involve treatment of the metal bisCbis(trimethy1sily1)amidol complex with the relevant areneselenol or tellurol in inert, nonpolar solvent using Schlenk techniques. The products precipitated and can be removed by filtration and recrystallized',2. TABLE 1. COMPLEXES FORMED FROM GROUPIB AND IIB COMPOUNDS WITH SELENOPHENOLS AND TELLUROPHENOLS Complex
Reaction
M(SeAr"), M = Zn, Cd; Ar" = 2 , 4 , 6 - ( B ~ - t ) ~ C ~ H , M(TeAr), M = Zn, Cd; Ar = 2,4,6-Me3C6HZ Cd[N(SiMe,),], CCd(TeAr),l, C6H,(Me),TeH NaSePh + CMe4NI2 W 4 (SePh110 1 M = Zn, Cd Zn(NO,), ' 6 H 2 0 + Me4NC1 M e H r 9 H Se(t-Bu)H Hg(CN), + Se(t-Bu)H CdZ' + PhSH + Et3N + NaTeH Cd2+ + PhSe- + NaSeH
Conditions Light petroleum for 1 h, warm slightly
1
Light petroleum for 4 h at - 10°C
1
+
+
Ref.
2 MeOH 60°C
3
MeOH at 0°C Et2O MeCN + EtOH
4 5 6
+ EtOH
6
MeCN
Caution: Hydrolysis of metal chalcogenolato complexes may lead to the liberation of chalcogenophenols and their decomposition products HzSe and H2Te, which have an unpleasant odor and are toxic. All preparations should be carried out in a well-ventilated fume hood. Selenophenol forms complexes isolatable as crystalline solids with both Zn and Cd nitrates. The salts [NMe4I2[Zn4(SePh)lo] and [NMe4I2[Cd4(SePh)lo] form when NaSePh reacts with Zn(N03)2.6 H 2 0 or Cd(N03)2.6 H 2 0 in MeOH solution3. The compounds are precipitated by addition of Me4NCl in MeOH, followed by MeCN. Also, the adduct MeSeHg0,CMe is prepared by distilling t-BuSeH in Et,O onto a solution of MeHgOH in MeOH at 0°C. The complex is also prepared from reaction between Hg(Me2Se2)and mercuric acetate in a H20/MeOH mixture4. 1. 2. 3. 4. 5. 6.
(E. M. PAGE) M. Bochmann, G. Bwembya, K. J. Webb, Inorg. Synth. 31, 19 (1997). U. Siemeling, Angew. Chem., Int. Ed. Engl., 32, 67 (1993). P. A. W. Dean, J. J. Vittal, N. C. Payne, Inarg. Chem., 26, 1683 (1987). A. P. Arnold, A. J. Canty, Inorg. Chim. Acta, 55, 171 (1981). J. W. Dale, H. J. Emeleus, R. N. Hazeldine, J . Chem. SOC., 2939 (1958). G. S. H. Lee, K. J. Fisher, D. C. Craig, M. L. Scudder, I. G. Dance, J . Am. Chem. Sac., 112, 6435 (1990).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 45 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.4 Reaction with Trimethylsilyl Chalcogenides 3.7.4.6.2.4 Reaction with Trimethylsilyl Chalcogenides. Another method of forming group I or IIB metal-chalcogen bonds involves reaction of a silyl chalcogenide with the metal compound. Silyl chalcogenides are stable and relatively easily prepared. They react with metal halides and oxyanions by exploiting the high oxophilicity and halophilicity of silicon'. The Li salt of HTeSi(SiMe3), reacts quantitatively with Zn-N and Zn-C bonds to afford tellurolysis and formation of Zn[TeSi(SiMe,),],'. The complexes "Me4]' [ Z I I ( S ~ P ~and ) ~ ]"Me4] [Cd(SePh)4] were obtained' by reaction of trimethylsilylselenophenol,NMe4C1, and tri-n-butylamine in MeOH with ZnCll or CdC12at RT (Table 1)2. A series of group IB selenolates, M[SeC(SiMe,),] (M = Cu, Ag), has been prepared using Li salts of trimethyl selenide314.The selenolates exhibit higher stability than the corresponding tellurolates as demonstrated by the ease of isolation of Cu,[SeC(SiMe,),], from a simple metathesis reaction using CuCl. The Ag complexes are obtained similarly starting from AgN0,. The Me3Si analogues are first examples of TABLE1. COMPLEXES FORMED BETWEEN GROUPIB TRIMETHYLSILYL LIGANDS Complex Zn[TeSi(SiMe,),l2 Zn[TeSi( SiMe,),].
AND
GROUPIIB METALCOMPOUNDS WITH
Reactants
Conditions
+
ZnEt, or Zn[N(SiMe,),], LiTeSi(SiMe,), ZnEt, or Zn[N(SiMe,),12 + HTeSi(SiMe,), Cd[N(SiMe3),I2 C6H2(Me),TeH M"(SiMe,),lz + HTeSi(SiMe3)3 HgClz + (THF),LiTeSi(SiMe,),
1
I
+
MMe,
+ PhESiMe,
Au4CEC(SiMe3),14 (E = Se, Te) Ph,PAu[TeC(SiMe,),]
(DME)LiSeC(SiMe,), + CuCl or AgN0, AuCI(THT) + LiEC(SiMe,), (1 : 1) LiTeC(SiMe,), Ph,PAuCI(l: 2) CuCl + PEt, + (Me,Si),Se
+
+ P(i-Pr), + (Me,Si),Se CuCl + P(t-Bu), + (Me3%),% CuCl + PEt, + (Me,Si),Se CuCl
I Hexane
8
E t 2 0 for 12 h
8 9
(1 : 2)
(CH,SiSePhH) + [NMe4]CI + MCl, HgXz + Me,SiCH,SeMe
Ref.
10, 11 MeOH
2
EtOH
12
DME for 1-3 h at RT C6Hrj for 2 h (Se) and 18 h (Te) EtzO for 24 h
3
Et,O at - 80 to - 20°C Et2O EtZO Et,O at - 80 to - 20°C
4 4
5 6
6 5
46 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.6 Reaction with Triphenylphosphine Chalcogenides
gold tellurolates obtained from metathesis reaction using AuCt(THT) as the metal source. A ~ ~ [ T e c ( S i M eexists ~ ) ~ las~ a tetramer in the solid state with a Te4Au4 core similar to that of c ~ ~ [ S e C ( S i M e ~ ) ~ l ~ . Reaction of CuCl with Me3Si chalcogenide ligands in the presence of tertiary phosphines is a route to the numerous copper chalcogenide megaclusters shown in Table 15' '. (E.
M. PAGE)
1. B. 0. Dabboussi, P. J. Bonasia, J. Arnold, J . Am. Chem. Soc., 113, 3186 (1991). 2. N. Ueyama, T. Sugawara, K. Sasaki, A. Nakamura, S. Yamashita, Y. Wakatsuki, H. Yamazaki, N. Yasuoka, Inorg. Chem., 27, 741 (1988). 3. P. J. Bonasia, G. P. Mitchell, F. J. Hollander, J. Arnold, Inorg. Chem., 33, 1797 (1994). 4. P. J. Bonasia, D. E. Gindelberger, J. Arnold, Inorg. Chem., 32, 5126 (1993). 5. D. Fenske, H. Krautscheid, Angew. Chem., Int. Ed. Engl., 29, 1452 (1990). 6. D. Fenske, H. Krautscheid, S. Balter, Angew. Chem., Int. Ed. Engl., 29, 796 (1990). 7. U. Siemelung, Angew. Chem., Int. Ed. Engl., 32, 67 (1993). 8. P. J. Bonasia, J. Arnold, Inorg. Chem., 31, 2508 (1992). 9. A. L. Seligson, P. J. Bonasia, J. Arnold, K.-M. Yu, J. M. Walker, E. D. Bourret, Proc. Muter. Res. Soc., 282, 665 (1992). 10. J. Arnold, Prog. Inorg. Chem., 43; 353 (1995). 11. S. M. Stuczynski, J. G . Brennan, M. L. Steigerwald, Inorg. Chem., 28, 4431 (1989). 12. R. K. Chada, J. E. Drake, N. T. McManus, A. Mislankar, Can. J . Chem., 65, 2305 (1987).
3.7.4.6.2.5 Reaction with Dialkylselenocarbamates. A series of Zn dialkyldiselenocarbamates, Zn[R2N CSeZl2(R = Me, Et, Bu), has been prepared from reaction between ZnS04 and the Na salt of the dialkyldiselenocarbamate in dioxane solution'. The copper complex, C U [ E ~ ~ N C Swas ~ ~obtained ]~, by shaking a CHC13 solution of the zinc derivative with aqueous CuS04' (Table l)','. TABLE1. COMPLEXES FORMED BETWEEN GROUPIB AND GROUPIIB COMPOUNDS WITH DIALKYLDISELENOCARBAMATE LIGANDS Complex
Reactants ~
Zn[R,NC(Se)Se], (R = Me, Et, Bu) Cu[Et ,NC(Se)Se]
ZnSO,
,
+ NaR2NCSe2
Zn[Et2NC(Se)Se12 iCuSO,
Conditions ~~
Ref. ~~
Dioxane
1
H2O
2 (E. M. PAGE)
1. D. Barnard, D. T. Woodbridge, J . Chem. Soc., 2922 (1961). 2. M. Bonamico, G. Dessy, J . Chem. Soc., A , 264 (1971).
3.7.4.6.2.6 Reaction with Triphenylphosphine Chalcogenides. Triphenylphosphine selenide, Ph3PSe, has been widely used in complex formation with group IIB compounds, resulting in adducts such as [ZnIz . Ph3PSeI and [HgXZ. Ph3PSel (Table l)'-'. The thermally stable but volatile compounds [M(t-BuzPSeNRz)] (M = Zn, Cd; R = i-Pr, C6Hll) are obtained by protolysis of Zn and Cd amides CM(N(siMe3)~)z-j with 2 equiv of phosphinochalcogenoic amides t-BuZPENHR. The X-ray crystal structure of the Zn compound has been determined'. Cations C(Ph3PSe)zAul' and [(Ph3PSe)AuPPh3]+ have been isolated as hexafluoroantimonate salts by reaction of equimolar amounts of Ph3PSe and THT. AuCl or
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
46 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.6 Reaction with Triphenylphosphine Chalcogenides
gold tellurolates obtained from metathesis reaction using AuCt(THT) as the metal source. A ~ ~ [ T e c ( S i M eexists ~ ) ~ las~ a tetramer in the solid state with a Te4Au4 core similar to that of c ~ ~ [ S e C ( S i M e ~ ) ~ l ~ . Reaction of CuCl with Me3Si chalcogenide ligands in the presence of tertiary phosphines is a route to the numerous copper chalcogenide megaclusters shown in Table 15' '. (E.
M. PAGE)
1. B. 0. Dabboussi, P. J. Bonasia, J. Arnold, J . Am. Chem. Soc., 113, 3186 (1991). 2. N. Ueyama, T. Sugawara, K. Sasaki, A. Nakamura, S. Yamashita, Y. Wakatsuki, H. Yamazaki, N. Yasuoka, Inorg. Chem., 27, 741 (1988). 3. P. J. Bonasia, G. P. Mitchell, F. J. Hollander, J. Arnold, Inorg. Chem., 33, 1797 (1994). 4. P. J. Bonasia, D. E. Gindelberger, J. Arnold, Inorg. Chem., 32, 5126 (1993). 5. D. Fenske, H. Krautscheid, Angew. Chem., Int. Ed. Engl., 29, 1452 (1990). 6. D. Fenske, H. Krautscheid, S. Balter, Angew. Chem., Int. Ed. Engl., 29, 796 (1990). 7. U. Siemelung, Angew. Chem., Int. Ed. Engl., 32, 67 (1993). 8. P. J. Bonasia, J. Arnold, Inorg. Chem., 31, 2508 (1992). 9. A. L. Seligson, P. J. Bonasia, J. Arnold, K.-M. Yu, J. M. Walker, E. D. Bourret, Proc. Muter. Res. Soc., 282, 665 (1992). 10. J. Arnold, Prog. Inorg. Chem., 43; 353 (1995). 11. S. M. Stuczynski, J. G . Brennan, M. L. Steigerwald, Inorg. Chem., 28, 4431 (1989). 12. R. K. Chada, J. E. Drake, N. T. McManus, A. Mislankar, Can. J . Chem., 65, 2305 (1987).
3.7.4.6.2.5 Reaction with Dialkylselenocarbamates. A series of Zn dialkyldiselenocarbamates, Zn[R2N CSeZl2(R = Me, Et, Bu), has been prepared from reaction between ZnS04 and the Na salt of the dialkyldiselenocarbamate in dioxane solution'. The copper complex, C U [ E ~ ~ N C Swas ~ ~obtained ]~, by shaking a CHC13 solution of the zinc derivative with aqueous CuS04' (Table l)','. TABLE1. COMPLEXES FORMED BETWEEN GROUPIB AND GROUPIIB COMPOUNDS WITH DIALKYLDISELENOCARBAMATE LIGANDS Complex
Reactants ~
Zn[R,NC(Se)Se], (R = Me, Et, Bu) Cu[Et ,NC(Se)Se]
ZnSO,
,
+ NaR2NCSe2
Zn[Et2NC(Se)Se12 iCuSO,
Conditions ~~
Ref. ~~
Dioxane
1
H2O
2 (E. M. PAGE)
1. D. Barnard, D. T. Woodbridge, J . Chem. Soc., 2922 (1961). 2. M. Bonamico, G. Dessy, J . Chem. Soc., A , 264 (1971).
3.7.4.6.2.6 Reaction with Triphenylphosphine Chalcogenides. Triphenylphosphine selenide, Ph3PSe, has been widely used in complex formation with group IIB compounds, resulting in adducts such as [ZnIz . Ph3PSeI and [HgXZ. Ph3PSel (Table l)'-'. The thermally stable but volatile compounds [M(t-BuzPSeNRz)] (M = Zn, Cd; R = i-Pr, C6Hll) are obtained by protolysis of Zn and Cd amides CM(N(siMe3)~)z-j with 2 equiv of phosphinochalcogenoic amides t-BuZPENHR. The X-ray crystal structure of the Zn compound has been determined'. Cations C(Ph3PSe)zAul' and [(Ph3PSe)AuPPh3]+ have been isolated as hexafluoroantimonate salts by reaction of equimolar amounts of Ph3PSe and THT. AuCl or
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
46 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.6 Reaction with Triphenylphosphine Chalcogenides
gold tellurolates obtained from metathesis reaction using AuCt(THT) as the metal source. A ~ ~ [ T e c ( S i M eexists ~ ) ~ las~ a tetramer in the solid state with a Te4Au4 core similar to that of c ~ ~ [ S e C ( S i M e ~ ) ~ l ~ . Reaction of CuCl with Me3Si chalcogenide ligands in the presence of tertiary phosphines is a route to the numerous copper chalcogenide megaclusters shown in Table 15' '. (E.
M. PAGE)
1. B. 0. Dabboussi, P. J. Bonasia, J. Arnold, J . Am. Chem. Soc., 113, 3186 (1991). 2. N. Ueyama, T. Sugawara, K. Sasaki, A. Nakamura, S. Yamashita, Y. Wakatsuki, H. Yamazaki, N. Yasuoka, Inorg. Chem., 27, 741 (1988). 3. P. J. Bonasia, G. P. Mitchell, F. J. Hollander, J. Arnold, Inorg. Chem., 33, 1797 (1994). 4. P. J. Bonasia, D. E. Gindelberger, J. Arnold, Inorg. Chem., 32, 5126 (1993). 5. D. Fenske, H. Krautscheid, Angew. Chem., Int. Ed. Engl., 29, 1452 (1990). 6. D. Fenske, H. Krautscheid, S. Balter, Angew. Chem., Int. Ed. Engl., 29, 796 (1990). 7. U. Siemelung, Angew. Chem., Int. Ed. Engl., 32, 67 (1993). 8. P. J. Bonasia, J. Arnold, Inorg. Chem., 31, 2508 (1992). 9. A. L. Seligson, P. J. Bonasia, J. Arnold, K.-M. Yu, J. M. Walker, E. D. Bourret, Proc. Muter. Res. Soc., 282, 665 (1992). 10. J. Arnold, Prog. Inorg. Chem., 43; 353 (1995). 11. S. M. Stuczynski, J. G . Brennan, M. L. Steigerwald, Inorg. Chem., 28, 4431 (1989). 12. R. K. Chada, J. E. Drake, N. T. McManus, A. Mislankar, Can. J . Chem., 65, 2305 (1987).
3.7.4.6.2.5 Reaction with Dialkylselenocarbamates. A series of Zn dialkyldiselenocarbamates, Zn[R2N CSeZl2(R = Me, Et, Bu), has been prepared from reaction between ZnS04 and the Na salt of the dialkyldiselenocarbamate in dioxane solution'. The copper complex, C U [ E ~ ~ N C Swas ~ ~obtained ]~, by shaking a CHC13 solution of the zinc derivative with aqueous CuS04' (Table l)','. TABLE1. COMPLEXES FORMED BETWEEN GROUPIB AND GROUPIIB COMPOUNDS WITH DIALKYLDISELENOCARBAMATE LIGANDS Complex
Reactants ~
Zn[R,NC(Se)Se], (R = Me, Et, Bu) Cu[Et ,NC(Se)Se]
ZnSO,
,
+ NaR2NCSe2
Zn[Et2NC(Se)Se12 iCuSO,
Conditions ~~
Ref. ~~
Dioxane
1
H2O
2 (E. M. PAGE)
1. D. Barnard, D. T. Woodbridge, J . Chem. Soc., 2922 (1961). 2. M. Bonamico, G. Dessy, J . Chem. Soc., A , 264 (1971).
3.7.4.6.2.6 Reaction with Triphenylphosphine Chalcogenides. Triphenylphosphine selenide, Ph3PSe, has been widely used in complex formation with group IIB compounds, resulting in adducts such as [ZnIz . Ph3PSeI and [HgXZ. Ph3PSel (Table l)'-'. The thermally stable but volatile compounds [M(t-BuzPSeNRz)] (M = Zn, Cd; R = i-Pr, C6Hll) are obtained by protolysis of Zn and Cd amides CM(N(siMe3)~)z-j with 2 equiv of phosphinochalcogenoic amides t-BuZPENHR. The X-ray crystal structure of the Zn compound has been determined'. Cations C(Ph3PSe)zAul' and [(Ph3PSe)AuPPh3]+ have been isolated as hexafluoroantimonate salts by reaction of equimolar amounts of Ph3PSe and THT. AuCl or
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 47 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.7 Reaction with Selenocyanate and Selenourea TABLE1. COMPLEXES FORMED FROMGROUPIB PHOSPHINE SELENIDES Complex ZnPh3PSe12 HgX,Ph,PSe (X = C1, Br, I) 3Hg(N03), 4Ph3PSe [HgCb(PPh3PS4l2 [Hg,X,(Ph,PSe)2l (n-Bu3PSe),MX2 (M = Hg, Cd; X = C1, Br, I) [M(t-Bu,PSeNR,)] (M = Zn, Cd; R = i-Pr, C,H,,) [A& (Ph2Se2141 [AsF, 1 2 [(Phd’Se)zAul [SbF61 [(Ph3PSe)Au(SePPh3)][SbF,]
AND
IIB COMPOUNDS BY REACTION WITH
Reaction
Conditions
ZnI, + Ph,PSe HgX, + Ph,PSe
3Hg(N03), + 4Ph,PSe HgC1, + Ph3PSe HgX2 + Ph3PSe (1 : 1) MX, + n-Bu,PSe t-Bu, PSeNHR + [M(N(SiMe3)2](2: 1) AgAsF, + Ph,Se, AuCl in THT + Ph3PSe (1 : 1) + AgSbF6 [(Ph3P)AuC1] + Ph3PSe + AgSbF, [(Ph3P)AuC1] + Se,(C,F,-4C1)Z AgSbF, HAuC1,/S02 + Ph,PSe
+
Ref.
5 5 Acetone EtOH 45 min at RT Liq SO2 CH2C12/Et20 for 1 h CHZC12for 1 h
1 5
2 2
3 MeOH
4
[(Ph3P)AuCl] in CHpC12/ether mixtures with Ph3PSe and solid AgSbF6. Products are obtained as colorless crystals after 1 h. X-ray studies show them to contain linear Au-Se linkages2. A similar method yields the cation [(Ph3P)2Au2Se(CgF4-4-C1)]+,isolated as the SbF; salt, which has Au atoms in close proximity3. Reaction of HAuC14 reduced by SO2 with PhsPSe yields AuCl Ph3PSe, which also has a linear Au-Se linkage4. (E. M. PAGE) 1. M. Bochmann, G. C. Bwembya, M. B. Hursthouse, S. J. Coles, J . Chem. Soc., Dalton Trans., 2813 (1995). 2. P. G. Jones, C. Thone, Inorg. Chim. Acta, 181, 291 (1991). 3. P. G. Jones, C. Thone, Z . Naturforsch., Teil B , 47, 600 (1992). 4. M. S . Hussain, J . Cryst. Spectrosc. Res., 16, 91 (1986). 5. T. S . Lobana, S. S . Sandhu, T. R. Gupta, J . Indian Chem. Soc., 58, 80 (1981). 6. M. G. King, G. P. McQuillan, J . Chem. SOC.,A , 898 (1967). 7. S . 0. Grim, E. D. Walton, L. C. Satek, Can. J . Chem., 58, 1476 (1980).
3.7.4.6.2.7 Reaction with Selenocyanate and Selenourea. Several complexes of Hg with selenocyanate and selenourea have been synthesized to promote an understanding of the effect of dietary Se in protecting against inorganic and organic mercurialsl,’. There is evidence from protein NMR studies that Se in selenocyanates and selenourea has a higher affinity for [MeHg]’ than does S in the corresponding thiocyanate or thiourea l i g a r ~ d s ~However ,~. until recently few complexes of organomercurials with Se ligands had been isolated and characterized. Table 1 lists complexes that have been studied and their preparation^^-'^.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 47 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.7 Reaction with Selenocyanate and Selenourea TABLE1. COMPLEXES FORMED FROMGROUPIB PHOSPHINE SELENIDES Complex ZnPh3PSe12 HgX,Ph,PSe (X = C1, Br, I) 3Hg(N03), 4Ph3PSe [HgCb(PPh3PS4l2 [Hg,X,(Ph,PSe)2l (n-Bu3PSe),MX2 (M = Hg, Cd; X = C1, Br, I) [M(t-Bu,PSeNR,)] (M = Zn, Cd; R = i-Pr, C,H,,) [A& (Ph2Se2141 [AsF, 1 2 [(Phd’Se)zAul [SbF61 [(Ph3PSe)Au(SePPh3)][SbF,]
AND
IIB COMPOUNDS BY REACTION WITH
Reaction
Conditions
ZnI, + Ph,PSe HgX, + Ph,PSe
3Hg(N03), + 4Ph,PSe HgC1, + Ph3PSe HgX2 + Ph3PSe (1 : 1) MX, + n-Bu,PSe t-Bu, PSeNHR + [M(N(SiMe3)2](2: 1) AgAsF, + Ph,Se, AuCl in THT + Ph3PSe (1 : 1) + AgSbF6 [(Ph3P)AuC1] + Ph3PSe + AgSbF, [(Ph3P)AuC1] + Se,(C,F,-4C1)Z AgSbF, HAuC1,/S02 + Ph,PSe
+
Ref.
5 5 Acetone EtOH 45 min at RT Liq SO2 CH2C12/Et20 for 1 h CHZC12for 1 h
1 5
2 2
3 MeOH
4
[(Ph3P)AuCl] in CHpC12/ether mixtures with Ph3PSe and solid AgSbF6. Products are obtained as colorless crystals after 1 h. X-ray studies show them to contain linear Au-Se linkages2. A similar method yields the cation [(Ph3P)2Au2Se(CgF4-4-C1)]+,isolated as the SbF; salt, which has Au atoms in close proximity3. Reaction of HAuC14 reduced by SO2 with PhsPSe yields AuCl Ph3PSe, which also has a linear Au-Se linkage4. (E. M. PAGE) 1. M. Bochmann, G. C. Bwembya, M. B. Hursthouse, S. J. Coles, J . Chem. Soc., Dalton Trans., 2813 (1995). 2. P. G. Jones, C. Thone, Inorg. Chim. Acta, 181, 291 (1991). 3. P. G. Jones, C. Thone, Z . Naturforsch., Teil B , 47, 600 (1992). 4. M. S . Hussain, J . Cryst. Spectrosc. Res., 16, 91 (1986). 5. T. S . Lobana, S. S . Sandhu, T. R. Gupta, J . Indian Chem. Soc., 58, 80 (1981). 6. M. G. King, G. P. McQuillan, J . Chem. SOC.,A , 898 (1967). 7. S . 0. Grim, E. D. Walton, L. C. Satek, Can. J . Chem., 58, 1476 (1980).
3.7.4.6.2.7 Reaction with Selenocyanate and Selenourea. Several complexes of Hg with selenocyanate and selenourea have been synthesized to promote an understanding of the effect of dietary Se in protecting against inorganic and organic mercurialsl,’. There is evidence from protein NMR studies that Se in selenocyanates and selenourea has a higher affinity for [MeHg]’ than does S in the corresponding thiocyanate or thiourea l i g a r ~ d s ~However ,~. until recently few complexes of organomercurials with Se ligands had been isolated and characterized. Table 1 lists complexes that have been studied and their preparation^^-'^.
48 3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.7 Reaction with Selenocyanate and Selenourea
TABLE1. COMPLEXES FORMED BETWEEN GROUPIB AND GROUPIIB METALCOMPLEXES WITH SELENOCYANATE AND SELENOUREA LIGANDS Complex [n-Bu,N],[Zn(NCSe),] [n-Bu4NI2[Cd2(NCSe)J H~CO(NCS~)~ [Ph,As] [Au(SeCN),] [Me,AuNCSe], Cu(NH3),(SeCN), . H 2 0 Cu(diamine),(SeCN), [MeHgSeC(NH,),]X (X = NO3, C104, C1, Br) HgC(NH2)2CSe12X, (X = C1, Br) C(Hg(NH2)CSe)C121z [Ph3PAuSeC(NH,),]C1
Reaction ZII(NO~+ ) ~KSeCN Cd(N0,)2 + KSeCN Hg(N0,)Z 2H20 Co(N03)2 6 H 2 0 + KSeCN [AuCl,]- + KSeCN ([Me,AuI], + AgI) + KSeNC Cu(N03), in NH,OH + KSeCN Bis(diamine)CuCl, + KSeCN MeHgX + SeC(NH,),
+
HgX,
+ (NH,),CSe
(1: 2)
HgClz + (NH2),CSe Ph3PAuC1 + (NH,),CSe
Conditions
Ref.
EtOH at - 20°C EtOH at - 20°C
5 5 11
Reflux under N2
12, 13 14 6 15 7
Acetone
8, 9
Acetone
8, 9 10
The complexes Rz [Zn(NCSe),] and Rz [Cd2NCSe)6] are prepared by treatment of metal nitrate EtOH solutions with ethanolic KSeCN[(n-C,H,),N] at - 20°C. Products were obtained as white crystals5. Reaction of ammoniacal C U ( N O ~ with ) ~ KSeCN yields the blue crystalline CU(NH~)~(S~C HzO, N ) ~which undergoes dehydration between 30 and 40"C6. Complexes [CH3HgSeC(NHz)z]X (X = N O 3 , ClO,, C1, Br) form by addition of hot deoxygenated aqueous solutions of MeHgX to a solution of selenourea under reflux and an atmosphere of NZ7.A similar reaction where selenourea reacts with HgC12 under reflux in a 2 : 1 molar ratio yields [Hg(NHz)2CSe]zX28*9. Dimer [(Hg(NHz)2CSe)C1z]z is obtained when excess HgClz is employed. Caution: Selenourea is extremely toxic and should be handled in an efficient fume hood or glovebox. Selenourea and Ph,PAuCl react to form [ P ~ , P A U S ~ = C ( N H ~ )which ~ ] C ~reacts , in aqueous sodium carbonate yielding (Ph3PAu)2Se.Further reaction with Ph3PAuC1and AgSbF6 produces the salt [(Ph3PAu)3Se][SbF6] lo. (E. M. PAGE) 1. H. W. Roesky,T. Gries, P. G. Jones, K. L. Weber, G. M. Sheldrick,J. Chem. Soc.,Dalton Trans., 1781 (1984). 2. H. E. Ganther, in Selenium, R. A. Zingaro, W. C. Cooper, eds., Van Nostrand, New York, 1974, p. 546. 3. D. L. Rabenstein, M. C. Tourangeau, C. A. Evans, Can. J . Chem., 54, 2517 (1976). 4. Y. Sugiura, Y. Hojo, Y. Tamai, H. Tanaka, J . Am. Chem. SOC.,98,2339 (1976). 5. J. L. Burmsteiner, L. E. Williams, Inorg. Chem., 5, 113 (1966). 6. V. V. Skopenko, G. V. Tsintsadze, Russ. J . Inorg. Chem., 9, 1442 (1962). 7. A. J. Carty, S. F. Malone, N. J. Taylor, J . Organamet. Chem., 172, 201 (1979). 8. G. B. Aitken, G. P. McQuillan, Inorg. Synth., 16, 83 (1976). 9. G. B. Aitken, J. L. Duncan, G. P. McQuillan, J . Chem. SOC.,A , 2103 (1972). 10. P. G. Jones, C. Thone, Chem. Ber., 124, 2725 (1991). 11. F. A. Cotton, D. M. L. Goodgame, M. Goodgame, T. E. Haas, Inorg. Chem., I, 565 (1962).
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 49 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.9 Reaction with Miscellaneous Ligands 12. 13. 14. 15.
M. S . Hussain, J . Cryst. Spectrosc., Res., 16, 91 (1986). H. Schmidtke, D. Garthoff, Helv. Chim. Acta, 50, 1631 (1967). F. Stocco, G. Stocco, W. M. Scovell, R. S. Tobias, Inorg. Chem., 10, 2639 (1971). M. E. Farago, J. M. James, Inorg. Chem., 4, 1706 (1965).
3.7.4.6.2.8 Reaction with Tetrahydroselenophene and Tetrahydrotellurophene and Derivatives. Tetrahydroselenophene (THSe) is used as a reagent to promote M-Se bond formation (Table 1). The complexes [(C4H8Se)2HgX2]can be prepared by direct reaction of HgX, with THSe and structurally characterized'. With HgBrz and HgIz, 1 : 2 complexes [HgX,(C4H8Se)Z] form'. 1,4-Diselenan (the Se analogue of 1,4-dioxane) forms derivatives with both Cu(1) and Cu(I1) of general formula CuCl . L and CuX, L (X = C1, Br)3. Difficulties in isolating crystalline phenyl telluride complexes led to a search for other more readily isolable organotellurides. The 2-tellurothiophene anion [C4H,STe]- reacts with AgN03 in D M F yielding [Ag4(TeC4H3S)6]2-4. TABLE1. COMPLEXES FORMED BETWEEN GROUP IB AND GROUP IIB COMPOUNDS WITH TETRAHYDROSELENOPHENE LIGANDS Complex [(C~H~WZH~XJ (X = Br, I) CHg(C4H,Se)lC12 CuCI[C,H,Se,) C~X~(C~HSS~Z) CPh4PIz CAg4(TeC4H S),l
Reactants HgX,
Conditions
Ref
+ C4H,Se
Warm MeCN
1
+
MeOH
2 3
DMF
4
HgCl2 C4H8Se CuCl or CuX, + C4H8Se, AgN03 + [Ph4P][C4H3STe]
(E. M. PAGE) 1. 2. 3. 4.
C. Stalhandske, F. Zintl, Acta Crystallogr., Sect. C , 44, 253 (1988). C. Stalhandske, F. Zintl, Acta Crystallogr., Sect. C , 42, 1449 (1986). P. J. Hendra, N. Sadasivan, J . Chem. SOC.,2063 (1965). J. Zhao, D. Adcock, W. T. Pennington, J. W. Kolis, Inorg. Chem., 29, 4358 (1990).
3.7.4.6.2.9 Reaction with Miscellaneous Ligands. Seleno derivatives of pyridine and dipyridyl are useful in formation of group IIB metal-selenium bond by reaction with metal salts','. These reactions, which yield volatile CVD precursors to group 11-VI semiconductors, are listed in Table 1 and discussed below (3.7.4.7). TABLE1. COMPOUNDS FORMED I N REACTIONS WITH MISCELLANEOUS LIGANDS Complex
Reactants
+ C Z ~ ( P Y S ~ S ~ P Y ) ( N O ~ ) ~PySeSePy I Zn(N03),6H20 PySeSePy + Hg(Ph), CHdPYSeSePy)(Ph)z1 M(L), HSeNC5H4 M(Se-2-NC5H4), L = 2-ethylhexanoate or (M = Cd, Hg) acetate ZnCl, + CSe, + Na [PPh4l2 CZn(C&)21 CPPh4I,CZn(CSe4)21
ZnC1,
Conditions
Ref.
Acetone for 3 h
2
+
E t 2 0 for 10min MeOH for 10 min
2 1 3
+ CSe, + Na
(MeOCH2CH2),0 solution at RT for 24 h DMSO for 8 h at RT
3
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 49 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.9 Reaction with Miscellaneous Ligands 12. 13. 14. 15.
M. S . Hussain, J . Cryst. Spectrosc., Res., 16, 91 (1986). H. Schmidtke, D. Garthoff, Helv. Chim. Acta, 50, 1631 (1967). F. Stocco, G. Stocco, W. M. Scovell, R. S. Tobias, Inorg. Chem., 10, 2639 (1971). M. E. Farago, J. M. James, Inorg. Chem., 4, 1706 (1965).
3.7.4.6.2.8 Reaction with Tetrahydroselenophene and Tetrahydrotellurophene and Derivatives. Tetrahydroselenophene (THSe) is used as a reagent to promote M-Se bond formation (Table 1). The complexes [(C4H8Se)2HgX2]can be prepared by direct reaction of HgX, with THSe and structurally characterized'. With HgBrz and HgIz, 1 : 2 complexes [HgX,(C4H8Se)Z] form'. 1,4-Diselenan (the Se analogue of 1,4-dioxane) forms derivatives with both Cu(1) and Cu(I1) of general formula CuCl . L and CuX, L (X = C1, Br)3. Difficulties in isolating crystalline phenyl telluride complexes led to a search for other more readily isolable organotellurides. The 2-tellurothiophene anion [C4H,STe]- reacts with AgN03 in D M F yielding [Ag4(TeC4H3S)6]2-4. TABLE1. COMPLEXES FORMED BETWEEN GROUP IB AND GROUP IIB COMPOUNDS WITH TETRAHYDROSELENOPHENE LIGANDS Complex [(C~H~WZH~XJ (X = Br, I) CHg(C4H,Se)lC12 CuCI[C,H,Se,) C~X~(C~HSS~Z) CPh4PIz CAg4(TeC4H S),l
Reactants HgX,
Conditions
Ref
+ C4H,Se
Warm MeCN
1
+
MeOH
2 3
DMF
4
HgCl2 C4H8Se CuCl or CuX, + C4H8Se, AgN03 + [Ph4P][C4H3STe]
(E. M. PAGE) 1. 2. 3. 4.
C. Stalhandske, F. Zintl, Acta Crystallogr., Sect. C , 44, 253 (1988). C. Stalhandske, F. Zintl, Acta Crystallogr., Sect. C , 42, 1449 (1986). P. J. Hendra, N. Sadasivan, J . Chem. SOC.,2063 (1965). J. Zhao, D. Adcock, W. T. Pennington, J. W. Kolis, Inorg. Chem., 29, 4358 (1990).
3.7.4.6.2.9 Reaction with Miscellaneous Ligands. Seleno derivatives of pyridine and dipyridyl are useful in formation of group IIB metal-selenium bond by reaction with metal salts','. These reactions, which yield volatile CVD precursors to group 11-VI semiconductors, are listed in Table 1 and discussed below (3.7.4.7). TABLE1. COMPOUNDS FORMED I N REACTIONS WITH MISCELLANEOUS LIGANDS Complex
Reactants
+ C Z ~ ( P Y S ~ S ~ P Y ) ( N O ~ ) ~PySeSePy I Zn(N03),6H20 PySeSePy + Hg(Ph), CHdPYSeSePy)(Ph)z1 M(L), HSeNC5H4 M(Se-2-NC5H4), L = 2-ethylhexanoate or (M = Cd, Hg) acetate ZnCl, + CSe, + Na [PPh4l2 CZn(C&)21 CPPh4I,CZn(CSe4)21
ZnC1,
Conditions
Ref.
Acetone for 3 h
2
+
E t 2 0 for 10min MeOH for 10 min
2 1 3
+ CSe, + Na
(MeOCH2CH2),0 solution at RT for 24 h DMSO for 8 h at RT
3
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.7.4.6 From Donor Ligands Incorporating the Elements Selenium and Tellurium 49 3.7.4.6.2 By Reactions with Metal Compounds 3.7.4.6.2.9 Reaction with Miscellaneous Ligands 12. 13. 14. 15.
M. S . Hussain, J . Cryst. Spectrosc., Res., 16, 91 (1986). H. Schmidtke, D. Garthoff, Helv. Chim. Acta, 50, 1631 (1967). F. Stocco, G. Stocco, W. M. Scovell, R. S. Tobias, Inorg. Chem., 10, 2639 (1971). M. E. Farago, J. M. James, Inorg. Chem., 4, 1706 (1965).
3.7.4.6.2.8 Reaction with Tetrahydroselenophene and Tetrahydrotellurophene and Derivatives. Tetrahydroselenophene (THSe) is used as a reagent to promote M-Se bond formation (Table 1). The complexes [(C4H8Se)2HgX2]can be prepared by direct reaction of HgX, with THSe and structurally characterized'. With HgBrz and HgIz, 1 : 2 complexes [HgX,(C4H8Se)Z] form'. 1,4-Diselenan (the Se analogue of 1,4-dioxane) forms derivatives with both Cu(1) and Cu(I1) of general formula CuCl . L and CuX, L (X = C1, Br)3. Difficulties in isolating crystalline phenyl telluride complexes led to a search for other more readily isolable organotellurides. The 2-tellurothiophene anion [C4H,STe]- reacts with AgN03 in D M F yielding [Ag4(TeC4H3S)6]2-4. TABLE1. COMPLEXES FORMED BETWEEN GROUP IB AND GROUP IIB COMPOUNDS WITH TETRAHYDROSELENOPHENE LIGANDS Complex [(C~H~WZH~XJ (X = Br, I) CHg(C4H,Se)lC12 CuCI[C,H,Se,) C~X~(C~HSS~Z) CPh4PIz CAg4(TeC4H S),l
Reactants HgX,
Conditions
Ref
+ C4H,Se
Warm MeCN
1
+
MeOH
2 3
DMF
4
HgCl2 C4H8Se CuCl or CuX, + C4H8Se, AgN03 + [Ph4P][C4H3STe]
(E. M. PAGE) 1. 2. 3. 4.
C. Stalhandske, F. Zintl, Acta Crystallogr., Sect. C , 44, 253 (1988). C. Stalhandske, F. Zintl, Acta Crystallogr., Sect. C , 42, 1449 (1986). P. J. Hendra, N. Sadasivan, J . Chem. SOC.,2063 (1965). J. Zhao, D. Adcock, W. T. Pennington, J. W. Kolis, Inorg. Chem., 29, 4358 (1990).
3.7.4.6.2.9 Reaction with Miscellaneous Ligands. Seleno derivatives of pyridine and dipyridyl are useful in formation of group IIB metal-selenium bond by reaction with metal salts','. These reactions, which yield volatile CVD precursors to group 11-VI semiconductors, are listed in Table 1 and discussed below (3.7.4.7). TABLE1. COMPOUNDS FORMED I N REACTIONS WITH MISCELLANEOUS LIGANDS Complex
Reactants
+ C Z ~ ( P Y S ~ S ~ P Y ) ( N O ~ ) ~PySeSePy I Zn(N03),6H20 PySeSePy + Hg(Ph), CHdPYSeSePy)(Ph)z1 M(L), HSeNC5H4 M(Se-2-NC5H4), L = 2-ethylhexanoate or (M = Cd, Hg) acetate ZnCl, + CSe, + Na [PPh4l2 CZn(C&)21 CPPh4I,CZn(CSe4)21
ZnC1,
Conditions
Ref.
Acetone for 3 h
2
+
E t 2 0 for 10min MeOH for 10 min
2 1 3
+ CSe, + Na
(MeOCH2CH2),0 solution at RT for 24 h DMSO for 8 h at RT
3
50
3.7 Formation of the Group VIB-Group IB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.7 By Reaction with Se or Te in MOCVD and Related Reactions
The complexes [PPh4I2[Zn(C3Se5)z] and [PPh4I2[Zn(CSe4j2] have been isolated from ZnClz reactions with a suspension of Na metal and CSez in solution3.
(E.M. PAGE) 1. Y. F. Cheng, T. J. Emge, J. G. Brennan, Inorg. Chem., 33, 3711 (1994). 2. C. 0. Kienitz, C. Thone, P. G. Jones, Inorg. Chem., 35, 3990 (1996). 3. G. Matasubayashi, K. Akiba, T. Tanaka, J . Chem. SOC.,Dalton Trans., 115 (1990).
3.7.4.7 By Reaction with Selenium or Tellurium Compounds in Metal-Organic Chemical Vapor Deposition (MOCVD) and Related Reactions The potential uses of binary Zn and Cd compounds with Se and Te in advanced electronic and optoelectronic devices has stimulated interest in syntheses of precursors for deposition of thin films of these materials, whose band gaps are compatible with light emission in the visible region. Potential uses of these Se and Te compounds in devices such as light-emitting diodes, optical waveguides and optical switches are being investigated. To function in such devices, the compounds must be deposited on a suitable substrate in very thin ( < 10 A) but extremely high quality single layers. Growth of such materials is achieved by metal-organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE). These processes are combined in metal-organic molecular beam epitaxy (MOMBE); the field has been well reviewed'-6. This section is not a thorough review but simply describes some of the reaction types that form the metal-chalcogen bond. Conventional MOCVD processes involve reaction of a group IIB metal dialkyl with HzSe or H2Te. Reaction occurs in the vapor phase where metal chalcogen bond formation occurs, and the alkyl group is removed as alkane. Table l 7 - I 5 lists some layer materials that have been prepared by these methods. Reactant vapors and any required dopant are introduced by means of an inert transport gas, over a suitable heated substrate where reaction occurs and the compound is deposited. To reduce contamination by products from prereactions with HzSe and HZTe, dialkyl chalcogenides have more recently been used as precursors. Excellent CdTe and HgTe layers are grown at temperatures as low as 220 and 230°C using di-tert-butyltelluride (t-BuzTe)I6. TABLE1. GROUPIIB-Se AND Te COMPOUNDS FORMED BY VAPORPHASE DEPOSITIOK METHODS Product
Reactants
ZnSe ZnSe ZnSe ZnTe CdSe CdTe CdTe HgTe HgTe Hg(i-,,,Cd,Te
Me2Zn Et2Zn R,Zn Et2Zn Me2Cd Me2Cd Me2Cd Hg Hg Me2Cd
H2Se H2Se R,Se Me2Te H2Se Me2Te Me(ally1)Te
+ Hg
MezTe Et2Te/Hz
Temperature ('C)
Ref.
200-500 500-700 200-500 500 600 500 250-350
7 8 9 10,ll 8 8 8 12,13
Heated CdTe substrate at 410°C
14 15
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
50
3.7 Formation of the Group VIB-Group IB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.7 By Reaction with Se or Te in MOCVD and Related Reactions
The complexes [PPh4I2[Zn(C3Se5)z] and [PPh4I2[Zn(CSe4j2] have been isolated from ZnClz reactions with a suspension of Na metal and CSez in solution3.
(E.M. PAGE) 1. Y. F. Cheng, T. J. Emge, J. G. Brennan, Inorg. Chem., 33, 3711 (1994). 2. C. 0. Kienitz, C. Thone, P. G. Jones, Inorg. Chem., 35, 3990 (1996). 3. G. Matasubayashi, K. Akiba, T. Tanaka, J . Chem. SOC.,Dalton Trans., 115 (1990).
3.7.4.7 By Reaction with Selenium or Tellurium Compounds in Metal-Organic Chemical Vapor Deposition (MOCVD) and Related Reactions The potential uses of binary Zn and Cd compounds with Se and Te in advanced electronic and optoelectronic devices has stimulated interest in syntheses of precursors for deposition of thin films of these materials, whose band gaps are compatible with light emission in the visible region. Potential uses of these Se and Te compounds in devices such as light-emitting diodes, optical waveguides and optical switches are being investigated. To function in such devices, the compounds must be deposited on a suitable substrate in very thin ( < 10 A) but extremely high quality single layers. Growth of such materials is achieved by metal-organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE). These processes are combined in metal-organic molecular beam epitaxy (MOMBE); the field has been well reviewed'-6. This section is not a thorough review but simply describes some of the reaction types that form the metal-chalcogen bond. Conventional MOCVD processes involve reaction of a group IIB metal dialkyl with HzSe or H2Te. Reaction occurs in the vapor phase where metal chalcogen bond formation occurs, and the alkyl group is removed as alkane. Table l 7 - I 5 lists some layer materials that have been prepared by these methods. Reactant vapors and any required dopant are introduced by means of an inert transport gas, over a suitable heated substrate where reaction occurs and the compound is deposited. To reduce contamination by products from prereactions with HzSe and HZTe, dialkyl chalcogenides have more recently been used as precursors. Excellent CdTe and HgTe layers are grown at temperatures as low as 220 and 230°C using di-tert-butyltelluride (t-BuzTe)I6. TABLE1. GROUPIIB-Se AND Te COMPOUNDS FORMED BY VAPORPHASE DEPOSITIOK METHODS Product
Reactants
ZnSe ZnSe ZnSe ZnTe CdSe CdTe CdTe HgTe HgTe Hg(i-,,,Cd,Te
Me2Zn Et2Zn R,Zn Et2Zn Me2Cd Me2Cd Me2Cd Hg Hg Me2Cd
H2Se H2Se R,Se Me2Te H2Se Me2Te Me(ally1)Te
+ Hg
MezTe Et2Te/Hz
Temperature ('C)
Ref.
200-500 500-700 200-500 500 600 500 250-350
7 8 9 10,ll 8 8 8 12,13
Heated CdTe substrate at 410°C
14 15
3.7 Formation of the Group VIB-Group IB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.7 By Reaction with Se or Te in MOCVD and Related Reactions
51
Relative stability of organochalcogen compounds is in the order. Me2Te > EtzTe, n-Pr2Te > i-PrzTe > f-BuzTe and depends on the strength of the C-E bond6. However, as stability of the organochalcogen molecule decreases, the molecules become heavier and their associated vapor pressures lower. Increased vapor pressures are observed when the branching is increased in organochalcogen compounds with higher numbers of C atoms. Thus high growth rates and low growth temperatures are obtained by increasing the concentrations of t-BuzTe. Lower stabilities are found in diallyl telluride, where delocalization of the free radical electron over the double bonds results in stabilization of the TC system and weakening of the C-Te bond. Methyl(ally1)telluride proves to be a useful precursor in formation of CdTe and HgTe. Its decomposition reactions have been studied in detail12,1 3 , ". Adducts of Zn and Cd alkyls find application as precursors in the growth of wide band gap group 11-VI semiconductors by MOCVD. Using adducts effectively allows a lower vapour pressure of metal alkyl to be used and limits prereaction before the reactants reach the hot zone of the reactor. Interest in group I1 metal complexes with selenolate and tellurolate ligands increased markedly upon discovery that CdTe and HgTe can be synthesized at relatively low temperatures by pyrolysis of [M(TePh)2], precursors". Main prerequisites for compounds as single molecule precursors are (1) relatively high volatility, (2) ready decomposition to the group 11-VI material without contamination by side products, (3) low toxicity, and (4) good control of film stoichiometry and growth rates. Besides the bischalcogenato complexes [M(ER)z],, (M = Zn, Cd, Hg; E = S, Se, Te), adducts with 1,2-bis(diethylphosphino)ethane (depe) such as [Cdz(SeC&)4(depe)], and [Hg(SeC6Hs)z(depe)]2 decompose upon pyrolysis to the bischal~ogenides'~. The goal is to prepare appropriate complexes, with sufficient volatility, that will decompose in a controlled manner to give the group 11-VI material. To enhance volatility and suppress polymer formation, sterically demanding chalcogenides of considerable bulk have been designed, to reduce the molecularity of the resulting complexes. A range of precursors for group 11-VI materials based on 2,4,6-tri-tevt-butylphenylchalcogenate has been developed, their syntheses are reported above (3.7.4.6.2)20-24.The general preparative route is:
M[N(SiMe3),12
+
2 f-Bu
t-Bu
(M
= Zn,
Cd)
/
52
3.7 Formation of the Group VIE-Group IB or llB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or IIB Elements 3.7.4.7 By Reaction with Se or Te in MOCVD and Related Reactions
M[N(SiMe3),12
-
(
+ 2 LiTe' + - t - B ) t-Bu t-Bu t-B~)2]2 + 2[LiN(SiMe3),]
[M(Te t-Bu
(M
= Zn, Cd)
(4
(E = Se, Te)
One problem with complexes having bulky aromatic ligands is the possibility that carbon will be incorporated into the films as a contaminant. Another drawback is that sterically saturated compounds tend to reductively eliminate dichalcogenide and to yield the metal rather than the metal dichalcogenide. This is especially problematic with the Hg analogues that decompose to atomic Hg and diary1 chalcogenides. Complexes M(Se-2-N5H& (M = Cd, Hg) prepared from reaction of Cd(II)(2-ethylhexanoate) or Hg(I1)acetate and pyridine-2-selenol (HSeNC5H4) dissolved in MeOH sublime without decomposition and decompose at higher temperatures to give solid state MSe layersz5. Precursors that contain bulky alkyl and silyl ligands -ESi(SiMe3)3 are more thermally stable. Systems of stoichiometry M[ESi(SiCH3)3]2 (M = Zn, Cd, Hg; E = S, Se, Te) yield the metal chalcogenide, at temperatures around 400cC26,27. These are potentially useful for deposition of MTe layers because aryl tellurolates are particularly thermally unstable and of low volatility. The complex Hg[TeSi(SiMe3)3]2 sublimes cleanly at ca. 150-200°C and decomposes at ca. 400°C to HgTe. As indicated earlier (3.7.4.6.2),the Te-containing ligand HSitel, HTeSi(SiMe3)3,is used in generation of metal tellurolates, as shown in equation (d)28,29: M [N(SiMe&]z
-
+ 2HTeSi(SiMe3)3
+
[M {TeSi(SiMe3)3}~]2 2HN(SiMe& (d)
(M = Zn, Cd, Hg) Compounds of general formula [M(TeSi(SiMe3)3}2]2 are volatile and easily manipulated under Nz. They sublime on heating, producing monomeric species that pyrolyze cleanly with deposition of thin films. Zinc telluride deposits from [Zn{TeSi(SiMe3)3}~]2 at temperatures of around 250-350°C onto quartz, silicon, InAs, and GaSb substrates and from CdTe onto silicon substrates.
3.7 Formation of the Group VIB-Group IB or IIB Metal Bond 3.7.4 Bond Between Se, Te, and Po and Group IB or llB Elements 3.7.4.7 By Reaction with Se or Te in MOCVD and Related Reactions
53
The alkyldiselenocarbamates are another series of complexes with potential as precursors for metal chalcogen deposition reactions at relatively low temperatures. The compounds can be prepared by an insertion reaction of CSez into the metal-Se bond3'. Through conproportionation reactions, mixed species such as methylcadmium/methylzinc diethyldiselenocarbamate are prepared from which it is possible to obtain thin films of the ternary solid Cdo.sZno.sSe: MezZn
+ Cd(Se2CNEtz)z
-
[MezCdZn(SezCNEtz)2]
(4 (E.M. PAGE)
1. R. J. M. Griffiths, Chem. Ind. (London),247 (1985). 2. P. OBrien, Precursors for Electronic Materials, in Inorganic Materials, D. Bruce, D. OHare, eds., Wiley, London, 1992, p. 499. 3. P. OBrien, R. Nomura, J . Mater. Chem., 5, 1761 (1995). 4. J. B. Mullin, S. J. C. Irvine, D. J. Ashen, J . Cryst. Growth, 55, 92 (1981). 5. B. Cockayne, P. J. Wright, in Growth and Optical Properties of Wide-Gap 11-Vl Low Dimensional Semiconductors, Plenum Press, New York, 1989, pp. 75-85. 6. H. B. Singh, N. Sudha, Polyhedron, 15, 745 (1996). 7. A. Yoshikawa, S. Yamaga, K. Tanaka, H. Kasai, J . Cryst. Growth, 72, 13 (1985). 8. H. M. Manasevit, W. I. Simpson, J . Electrochem. Soc., 118, 644 (1971). 9. P . Blanconnier, J. F. Hogrel, A. M. Jean-Louis, B. Sermage, J . Appl. Phys., 52, 6895 (1981). 10. S. Sritharan, K. A. Jones, J . Cryst. Growth, 66, 231 (1984). 11. H. Mitsuhashi, I. Mitsuishi, H. Kukimoto, Jap. J . Appl. Phys., 24, L864 (1984). 12. J. E. Hails, D. J. Cole-Hamilton, W. Bell, J . Cryst. Growth, 145, 596 (1994). 13. S. K. Gandhi, I. B. Bhat, H. Ehsani, D. Nucciarone, G. Miller, Appl. Phys. Lett., 55, 137 (1989). 14. T. F. Keuch, J. 0. McCaldin, J . Electrochem. SOC., 128, 1142 (1981). 15. J. B. Mullin, S. J. C. Irvine, J . Phys. D,Appl. Phys. 14, L149 (1981). 16. W. E. Hoke, P. J. Lemonias, Appl. Phys. Lett., 48, 1669 (1986). 17. J. D. Parsons, L. S. Lichtmann, J . Appl. Phys., 86, 222 (1988). 18. M. L. Steigerwald, C. R. Sprinkle, J . Am. Chem. Soc., 109, 7200 (1987). 19. J. G. Brennan, T. Segrist, P. J. Carroll, S. M. Stuczynski, P. Reynders, L. E. Brus, M. L. Steigerwald, J . Am. Chem. Soc., 111, 4141 (1989); Chem. Mater., 2, 403 (1990). 20. M. Bochmann, K. Webb, M. Harman, M. B. Hursthouse, Angew. Chem., In?. Ed. Engl., 29, 638 (1990). 21. M. Bochmann, K. Webb, M. B. Hursthouse, M. Mazid, J . Chem. Soc., Dalton Trans., 2317 (1991). 22. M. Bochmann, K. Webb, J . Chem. SOC.,Dalton Trans., 2325 (1991). 23. M. Bochmann, G. C. Bwembya, R. Grinter, A. K. Powell, K. J. Webb, M. B. Hursthouse, K. M. Abdel Malik, M. A. Mazid, Inorg. Chem., 33, 2290 (1994). 24. M. Bochmann, G. Bwembya, K. J. Webb, Inorg. Synth., 31, 19 (1997). 25. Y . F. Cheng, T. J. Emge, J. G. Brennan, Inorg. Chem., 33, 3711 (1994). 26. B. 0. Dabbousi, P. J. Bonasia, J. Arnold, J . Am. Chem. SOC.,113, 3186 (1991). 27. P. J. Bonasia, J. Arnold, Inorg. Chem., 31, 2508 (1992). 28. P. J. Bonasia, D. E. Gindelberger, B. 0.Dabbousi, J. Arnold, J . Am. Chem. Soc., 114,5209 (1992). 29. P. J. Bonasia, G. P. Mitchell, F. J. Hollander, J. Arnold, Inorg. Chem., 33, 1797 (1994). 30. M. B. Hursthouse, M. A. Malik, M. Montevalli, P. OBrien, Organometallics, 10, 730 (1991).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8 Formation of Bonds Between the Group VIB
(0,S, Se, Te, Po) Elements and Transition and Inner Transition Metals 3.8.1 Introduction This section covers reactions by which bonds between the group VIB elements (0,S, Se, Te, and Po) and the transition elements are formed. As with the coverage in Section 3.7, a large area of synthetic chemistry is represented, because bond formation of these types occurs in the contexts of inorganic, organometallic, and materials chemistry. (A. D. NORMAN)
3.8.2 Formation of the Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.1 By Reaction with the Transition or Inner Transition Metal
Transition metals react directly with O2to form metal-oxygen At RT bulk metal samples often form surface oxide layers that prevent further reaction. Finely divided samples of Fe, Co, and Ni, however, are pyrophoric in 0,. At elevated temperatures, typically red heat, high surface area metal powders combine with 0, forming binary oxides. The most common transition metal oxides are listed in Table 1 6 s 7 . Those resulting from direct reaction of the metal with molecular 0, are shown in bold face. Formation of transition metal oxides in cryogenic matrices has also been reported. Laser-ablated Fe atoms condensed with O 2 in Ar matrices form OFeO, FeOO, and Fe(02), identified by IR spectroscopy'. Similar studies have been carried out on metal atoms of groups IVA9 and VIII'o-'2. Gas phase Fe a t o m ~ ' ~ and ' ' ~ Fe c l u ~ t e r s 'also ~ react with 0,; e.g., gas-phase Fe atoms react with O2 to form Fe0214 and with O3 to form FeO 0 ~ ' ~ . Formation of metal-oxygen bonds at metal surfaces in ultra high vacuum has been reviewed",". The lanthanides are all electropositive and readily form oxide layers upon exposure to oxygen'-5. At elevated temperatures most combine with molecular 0, forming oxides with the stoichiometry Ln203.Cesium, however, reacts with 0, to form CeO, while Pr and T b form nonstoichiometric oxides with the approximate formulas P r 6 0 1 1 and T b 4 0 7 . Oxides with the general formula LnO are obtained by reduction of the higher oxides.
+
(W. S. DURFEE)
54
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
55
TABLE1. TRANSITION METALOXIDES sc
Scz03
Y
Yz03
La
V
Ti203, Ti305, Ti407, TiO,
Vz03, VO,,
Zr
Nb
Mo
Zr0,
NbO NbO2, NbO,
MOO,, MOO,
Ta
W
Hf
V205
~~~~~
La203
Mn
Ti
Cr
Crz03, MnO, CrO,, Mn304, Cr03 Mn203, MnO,, Mn207 Tc
Re ~~
HfO,
Ta02, Ta,O,
TcOz, Tc03, TczO,
WOz, W03
co
Ni
COO, Co304, Co203, Cooz
NiO
Ru
Rh
Pd
RuO,,
Rh,O,,
PdO
Fe
Fe,04 T=500”C Fe203 T>500”C
RuO~
Rho2
0s
Ir
Pt
OsO,, Os04
Irz03,
PtO Pt02
~
ReO,, Re205, ReO,,
IrO,
Re207 1. 2. 3. 4. 5.
6. 7.
8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.
N. N. Greenwood, A. Earnshaw, Chemistry o f t h e Elements, Pergamon Press, Oxford, 1984. B. Moody, Comparative Inorganic Chemistry, 3rd ed., Edward Arnold, London, 1991. F. A. Cotton, G. Wilkinson, Adcanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. J. D. Lee, Concise Inorganic Chemistry, 5th ed., Chapman & Hall, London, 1996. A. G. Sharpe, Inorganic Chemistry, 3rd ed., Longman, Essex, 1992. P. A. Cox, Transition Metal Oxides: An Introduction to Their Electronic Structure and Properties, Clarendon Press, Oxford, 1992. A. Wold, K. Dwight, Solid State Chemistry: Synthesis, Structure and Properties ofselected Oxides and Suljides, Chapman & Hall, New York, 1993. L. Andrews, G. V. Chertihin, C. W. Bauschlicher, J. Am. Chem. Soc., 118, 467 (1996). G. V. Chertihin, L. J. Andrews, J . Phys. Chem., 99, 6356 (1995). R. J. Van Zee, Y. M. Harmick, W. Weltner, Jr., J . Phys. Chem., 96, 7247 (1992). A. H. Hanlan, G. A. Ozin, Inorg. Chem., 16, 2848 (1977). A. H. Hanlan, G. A. Ozin; Inorg. Chem., 16, 2857 (1977). S. A. Mitchell, P. A. Hackett, J . Chem. Phys., 93, 7822 (1990). M. Helmer, J. M. C. Plane, J. Chem. Soc., Faraday Trans., 90, 395 (1994). R. L. Whetten, D. M. Cox, D. J. Trevor, A. Kaldor, J . Phys. Chem., 89, 566 (1985). M. Helmer, J. M. C. Plane: J. Chem. Soc., Faraday Trans., 90, 31 (1994). F. Besenbacher, J. K. N@skov,Prog. Surf Sci., 44, l(1993). G. H. Vurens, M. Salmeron, G. A. Somerjai, Prog. Surf Sci., 32, 333 (1989).
3.8.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
Transition metal complexes react with oxygen, changing the oxidation state of the metal with no formation of an oxygen-metal bond; this is the preferred mode for inner transition metals. When a product containing an oxygen-metal bond does result, it almost always retains an intact O2 group. The study of oxygen-binding to metal complexes’-5 is largely due to the emergence of bioinorganic chemistry and the
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
55
TABLE1. TRANSITION METALOXIDES sc
Scz03
Y
Yz03
La
V
Ti203, Ti305, Ti407, TiO,
Vz03, VO,,
Zr
Nb
Mo
Zr0,
NbO NbO2, NbO,
MOO,, MOO,
Ta
W
Hf
V205
~~~~~
La203
Mn
Ti
Cr
Crz03, MnO, CrO,, Mn304, Cr03 Mn203, MnO,, Mn207 Tc
Re ~~
HfO,
Ta02, Ta,O,
TcOz, Tc03, TczO,
WOz, W03
co
Ni
COO, Co304, Co203, Cooz
NiO
Ru
Rh
Pd
RuO,,
Rh,O,,
PdO
Fe
Fe,04 T=500”C Fe203 T>500”C
RuO~
Rho2
0s
Ir
Pt
OsO,, Os04
Irz03,
PtO Pt02
~
ReO,, Re205, ReO,,
IrO,
Re207 1. 2. 3. 4. 5.
6. 7.
8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.
N. N. Greenwood, A. Earnshaw, Chemistry o f t h e Elements, Pergamon Press, Oxford, 1984. B. Moody, Comparative Inorganic Chemistry, 3rd ed., Edward Arnold, London, 1991. F. A. Cotton, G. Wilkinson, Adcanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. J. D. Lee, Concise Inorganic Chemistry, 5th ed., Chapman & Hall, London, 1996. A. G. Sharpe, Inorganic Chemistry, 3rd ed., Longman, Essex, 1992. P. A. Cox, Transition Metal Oxides: An Introduction to Their Electronic Structure and Properties, Clarendon Press, Oxford, 1992. A. Wold, K. Dwight, Solid State Chemistry: Synthesis, Structure and Properties ofselected Oxides and Suljides, Chapman & Hall, New York, 1993. L. Andrews, G. V. Chertihin, C. W. Bauschlicher, J. Am. Chem. Soc., 118, 467 (1996). G. V. Chertihin, L. J. Andrews, J . Phys. Chem., 99, 6356 (1995). R. J. Van Zee, Y. M. Harmick, W. Weltner, Jr., J . Phys. Chem., 96, 7247 (1992). A. H. Hanlan, G. A. Ozin, Inorg. Chem., 16, 2848 (1977). A. H. Hanlan, G. A. Ozin; Inorg. Chem., 16, 2857 (1977). S. A. Mitchell, P. A. Hackett, J . Chem. Phys., 93, 7822 (1990). M. Helmer, J. M. C. Plane, J. Chem. Soc., Faraday Trans., 90, 395 (1994). R. L. Whetten, D. M. Cox, D. J. Trevor, A. Kaldor, J . Phys. Chem., 89, 566 (1985). M. Helmer, J. M. C. Plane: J. Chem. Soc., Faraday Trans., 90, 31 (1994). F. Besenbacher, J. K. N@skov,Prog. Surf Sci., 44, l(1993). G. H. Vurens, M. Salmeron, G. A. Somerjai, Prog. Surf Sci., 32, 333 (1989).
3.8.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
Transition metal complexes react with oxygen, changing the oxidation state of the metal with no formation of an oxygen-metal bond; this is the preferred mode for inner transition metals. When a product containing an oxygen-metal bond does result, it almost always retains an intact O2 group. The study of oxygen-binding to metal complexes’-5 is largely due to the emergence of bioinorganic chemistry and the
56
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
concomitant interest in models for the binding of oxygen in biological systems. Thus the largest emphasis has been on complexes that bind oxygen re~ersibly'-~. The formation of simple adducts by reaction of transition metal complexes with dioxygen, either from air or as gas, is limited to the nine group VIII metals plus manganese and chromium'~~. The four limiting cases of metal-oxygen binding are shown in Scheme 1" '. Only cobalt forms complexes of all four types. The prototype compound for type Ia binding is hemoglobin, which serves as an oxygen transport system in vertebrates6. Many iron-porphyrin model compounds have been to characterize this binding mode. Other metals can be substituted for the iron in hemoglobin and its models without loss of oxygen-binding ability. Chromium', cobalt', and rutheniumg complexes have the same (type Ia) binding mode. Type IIa is the most widespread one", and its prototype is Ir(CO)C1(PPh3)211.Like this compound, most complexes that form dioxygen adducts of this type are low-valent, coordinatively unsaturated, 16-electron complexes that undergo a formal oxidative addition to bind the oxygen. The relative rates and reversibility of dioxygen uptake are critically dependent on changes in substituents on both the metal12'l 3 and the phosphine ligands". Tetraphenylporphinatomanganese(I1)complexes, Mn(TPP)L, also bind oxygen in this f a ~ h i o n ' ~ .
Scheme 1. Type of metal-dioxygen binding Mononuclear
Dinuclear"
I
Ib
M
Ia
IIb
IIa
a
Dihedral angles are not shown as they vary considerably.
W Scheme 2. Co(Sa1en)
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.2 By Addition to Low-Valent and Unsaturated Metal Complexes
/-
57
The best illustrations for types Ib and IIb are the extensively studied cobalt systems', 5 , CW)
+O
4 (o;)co(III) Ia
+Co(II)
~~~~~~~~~~-~~~~~~~~
/
IIb
(a)
co(III)(o;)co(III) IIa The first intermediate seems to be a type Ia compound, which reacts with a second Co(I1) to yield a peroxo dimer, IIb. The only known route to superoxo-bridged complexes, Ib, is the oxidation of type IIb dimers. In most cases type IIb binding is reversible, but irreversible binding is also found". Additional bridging ligands, such as hydroxide, may also be present in these dinuclear compounds'5,'6. While most studies of oxygen addition have been performed on metal complexes in aqueous and nonaqueous solution, some complexes absorb oxygen even in the solid state, e.g., the Schiff base complexes of cobalt(I1)". Derivatives of Co(Sa1en)(Scheme 2) are used as solid state absorbers for separating oxygen from air'9120. Manganese tertiary phosphine halide complexes, MnLX2, also show reversible solid state dioxygen binding2'. A novel way of sequestering transition metal complexes to improve their oxygenbinding characteristics is to attach them to a polymeric backbone. With iron porphyrins, this approach increases capacity and rate of ~ p t a k e ~ and ' . ~ inhibits ~ formation of inactive p o x 0 d i m e r ~which ~ ~ , plague solution studies of many heme analogues. A better oxygen capacity per gram is attained by a familiy of polymeric oxime l i g a n d ~ ' ~whose .~~ Fe, Co, Ni, and Pd complexes reversibly bind oxygen. With ozone, most metal complexes react to produce only oxidized metal species. Two exceptions are the stoichiometric ozonation of trace amounts of Fe(CO)5 in gas streams to form FeC0327 and the formation of the hydroxide-bridged dimer C O ~ ( O ~ C C H ~ ) ~ ( O H ) ~ ( Hfrom O ~ Cthe CH ozonation ~) of cobalt (11) acetate in glacial acetic acid28. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.
(H. 8.ABRAHAMSON) L. Vaska, Ace. Chem. Res., 9, 175 (1976). R. W. Erskine, B. 0. Field, Struct. Bonding (Berlin),28, 1 (1976). F. Basolo, B. M. Hoffman, J. A. Ibers, Ace. Chem. Res., 8, 384 (1975). R. D. Jones, D. A. Summerville, F. Basolo, Chem. Ren., 79, 139 (1979). G. McLendon, A. E. Martell, Coord. C h e i . Ren., 19, 1 (1976). E. Antonini, M. Brunori, Hemoglobin and Myoglobin in Their Reactions with Ligands, North Holland, Amsterdam, 1971. S. K. Cheung, C. J. Grimes, J. Wong, C. A. Reed, J. Am. Chem. SOC.,98, 5028 (1976). T. Yonetani, H. Yamamoto, T. Iizuka, J . Biol. Chem., 249, 2168 (1974). N. Farrell, D. H. Dolphin, B. R. James, J. Am. Chem. Soc., 100, 324 (1978). V. J. Choy, C. J. O'Connor, Coord. Chem. Rev., 9, 145 (1972/1973). L. Vaska, Science, 140, 809 (1963). C. A. Reed, W. R. Roper, J. Chem. Soc., Dalton Trans., 1370 (1973). C. A. McAuliffe, R. Pollock, J . Organomet. Chem., 77, 265 (1974). F. Basolo, R. D. Jones, D. A. Summerville, Acta. Chem. Scand., A32, 771 (1978). A. G. Sykes, J. A. Weil, Prog. Inorg. Chem., 13, l(1970). R. G. Wilkins, Adc. Chem. Ser., 100, 111 (1971). G. Henrici-Olive, S. Olive, J . Organomet. Chem., 52, C49 (1973). M. R. Paris, D. Aymes, Bull. SOC. Chim. Fr., 1431 (1976).
58
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
19. B. B. Fogler, Ind. Eng. Chem., 39, 1353 (1947). 20. E. J. Boscola, J . Aircr., 11, 444 (1974). 21. C. A. McAuliffe, H. Al-Khateeb, M. H. Jones, W. Levason, K. Minten, F. P. McCullough, J . Chem. SOC.,Chem. Commun.,736 (1979). 22. E. Tsuchida, K. Honda, H. Sata, Biopolymers, 13, 2147 (1974). 23. E. Tsuchida, K. Honda, Polym. J., 7, 498 (1975). 24. 0.Leal, D. L. Anderson, R. G. Bowman, F. Basolo, R. L. Burwell, Jr.,J. Am. Chem. Soc., 97,5125 (1975). 25. H. Yukimasa, H. Sawai, T. Takizawa, Makromol. Chem., 180, 1681 (1979). 26. S. J. Kim and T. Takizawa, Makromol. Chem., 179, 531 (1978). 27. H. Callighan, J. 0. Hawthorne, U. S. Patent 3,780,163; Chem. Abstr., 80, 1 3 5 7 6 3 ~(1974). 28. S. S. Lande, C. D. Falk, J. K. Kochi, J . Inorg. Nucl. Chem., 33, 4101 (1971). 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
Most oxygen insertion reactions make use of oxygen atom transfer reagents, such as iodosylbenzene, PhIO. Reactions in which the inserted atom is derived from one of the are less common than CO, olefin, or SO2 two allotropic forms of oxygen, either O2 or 03, insertion reactions. Several oxygen insertion reactions involving group IVA’-’ and VA6 metal-alkyl complexes have been reported. Methyl complexes of Ti, Zr, and Hf with the ancillary ligand (t-Bu),CO- (tritox) form alkoxide complexes when exposed to 0 2 : (tritox),M(CH,),
0 2
(trit~x),M(OCH,)~
(M = Ti, Zr, Hf) 0
(trit~x)Ti(CH,)~ 2 , ( t r i t ~ x ) T i ( C H-,(OCH3), ~)~
n = 1-3
(b)
Inclusion of an allylic alkoxide in the metal coordination sphere, as in 1, provides evidence for alkylperoxide intermediates. Exposure of 1 to O2 results in both oxygen insertion into the M-CH3 bond and epoxidation of the terminal olefin. Epoxidation is due to 0 atom transfer from the methylperoxide intermediate’s3.
(M = Zr, Hf )
(c)
2
1
Oxygen insertion into the Zr-CH, reported2.
3
bond in ( V ~ - C ~ H ~ ) ~ Z 3, ~ (has C Halso ~ ) ~been ,
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
58
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
19. B. B. Fogler, Ind. Eng. Chem., 39, 1353 (1947). 20. E. J. Boscola, J . Aircr., 11, 444 (1974). 21. C. A. McAuliffe, H. Al-Khateeb, M. H. Jones, W. Levason, K. Minten, F. P. McCullough, J . Chem. SOC.,Chem. Commun.,736 (1979). 22. E. Tsuchida, K. Honda, H. Sata, Biopolymers, 13, 2147 (1974). 23. E. Tsuchida, K. Honda, Polym. J., 7, 498 (1975). 24. 0.Leal, D. L. Anderson, R. G. Bowman, F. Basolo, R. L. Burwell, Jr.,J. Am. Chem. Soc., 97,5125 (1975). 25. H. Yukimasa, H. Sawai, T. Takizawa, Makromol. Chem., 180, 1681 (1979). 26. S. J. Kim and T. Takizawa, Makromol. Chem., 179, 531 (1978). 27. H. Callighan, J. 0. Hawthorne, U. S. Patent 3,780,163; Chem. Abstr., 80, 1 3 5 7 6 3 ~(1974). 28. S. S. Lande, C. D. Falk, J. K. Kochi, J . Inorg. Nucl. Chem., 33, 4101 (1971). 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
Most oxygen insertion reactions make use of oxygen atom transfer reagents, such as iodosylbenzene, PhIO. Reactions in which the inserted atom is derived from one of the are less common than CO, olefin, or SO2 two allotropic forms of oxygen, either O2 or 03, insertion reactions. Several oxygen insertion reactions involving group IVA’-’ and VA6 metal-alkyl complexes have been reported. Methyl complexes of Ti, Zr, and Hf with the ancillary ligand (t-Bu),CO- (tritox) form alkoxide complexes when exposed to 0 2 : (tritox),M(CH,),
0 2
(trit~x),M(OCH,)~
(M = Ti, Zr, Hf) 0
(trit~x)Ti(CH,)~ 2 , ( t r i t ~ x ) T i ( C H-,(OCH3), ~)~
n = 1-3
(b)
Inclusion of an allylic alkoxide in the metal coordination sphere, as in 1, provides evidence for alkylperoxide intermediates. Exposure of 1 to O2 results in both oxygen insertion into the M-CH3 bond and epoxidation of the terminal olefin. Epoxidation is due to 0 atom transfer from the methylperoxide intermediate’s3.
(M = Zr, Hf )
(c)
2
1
Oxygen insertion into the Zr-CH, reported2.
3
bond in ( V ~ - C ~ H ~ ) ~ Z 3, ~ (has C Halso ~ ) ~been ,
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
59
Exposure of the Ta complex 4 to O2 yields a mixture of products, including the structurally characterized alkodide dimer 5 6 .
TaLdCH3)3
-
OCH3 OCH3 CH3
0:
L= OCH3
OCH3
5
4
Reaction of ( V ~ - C ~ M 6, ~ with ~ ) ~O2 V ,yields the near quantitative formation of the structurally characterized V(V) alkoxide-bridged dimer 7 ' ~ ~ . 0
7
6
Oxygen insertion into metal-CO bonds has been reported. The anionic complex [Et4N] [(y5-C5H5)Mo(CO),], 8, reacts with O2 forming the carbonate complex 1, [EhNI [(Y5-C5H5)Mo(CO)2(y2-ozco)
8
9
Similar reactivity is observed for the neutral dimer [(y5-CSMe5)Mo(CO)]2,10. When exposed to O2 in CH2C12under UV irradiation, the p-bicarbonato dimer [(y5C5Me5)Mo12(p-C1)( p-C03H)(p-O), (11) forms. Solvent is the source of the chloride 1igand'O.
10
11
60 3.8.2Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1From Dioxygen and Ozone 3.8.2.1.3By Insertion into Metal-Ligand Bonds Insertion into metal-P bonds is observed in the metal-metal-bonded Mo dimer 12". Under N2 atmosphere and lOppm of O2 oxygen inserts into the phosphide-Mo bond, forming the p o x 0 tetramer 13 as a minor product.
(CO)CpMo=MoCp(CO)
\ /
P Ph2 12
N, 0,
13
Under a CO atmosphere and trace 02, 12 is converted to the p o x 0 dimer 14 in 45% yield.
12
14
Similar reactivity of bridging phosphide groups is observed for the Rh dimer [Cp*Rh(PMez)] z, 15' '. CP *
CP *
/cp*
\ Rh-
,dr
\
0 2
__f
Me'\
P
1\
Me Me 15
Me
/cp*
\ '., i, Rh
Rh-
P- P\-o
I \
Me/deMe
(k)
Me
Alkyl complexes of Fe(II1)TTP (TTP = tetra-p-tolylporphyrin) react with O2 to form alkylperoxide complexes stable at - 70°C for several h o ~ r s ' ~They . decompose to (TTP)Fe3+OHand ultimately the p o x 0 dimer [(TTP)Fe3+I20.
Oxygen reacts with aryl Fe(II1) porphyrins to form phenoxide complexes, although arylperoxides are thought to be intermediate^'^. Several Co(II1) alkyl complexes with macrocyclic and chelating ligands have been O2 studied for their reactivity with 0 2 .Both thermall5-" and photochemical'"''
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
61
insertion into the Co-C bond of Co(II1)-alkyl complexes resulting in the formation of Co-alkylperoxide species have been r e p ~ r t e d '2~0 '. When ( -)-R-(2-0ctyl)Co(dmgH)~py, 16, is exposed to O2 under UV irradiation, a racimized alkylperoxide Co(II1) complex results".
yio<;xy;;o<;x I (-)R
I
-
Py
O - y y
o,
HY:-('IR
1
0
I
1
2%
(R=2-octyU
))
I
Ty
0% H,
))
(m)
16 A mechanistic study of the photochemical insertion of O 2 into Co(I1)-alkylporphyrins suggests that Co-C bond homolysis is the first step".
+
(4
Co(III)(P)(R)(L)+ Co(II)(P)(L) R* R*
+
-
02-
Co(II)(P)(L)+ ROO.
ROO.
Co(III)(P)(OOR)(L)
(R = CH3, C2H5,CH2C6H5;P = T P P or OEP, L 1-methylimidazole or PR3) Oxygen inserts into one of the Ir-C COD)Ir(P309)],17, forming 18".
17
=
(0)
C5H5N,
bonds of the complex [Bu4N],[(y4-
18
Peroxocarbonate complexes are obtained by O2 insertion into M-C02 bonds. The Ni-C02 complex Ni(q2-C02){P(C6H11)3}2, 19, reacts forming the complex Ni(y2Co4) { p ( c 6 ~ l l ) 3 } 2oZ3. 2,
19
20
The macrocyclic Ni complex of the cyclam ligand (cyclam = 1,4,8,1l-tetraazacyclotetradecane) forms the methyl-Ni(II1) complex 21 when exposed to CH3 radicals
62
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 From Dioxygen and Ozone 3.8.2.1.3 By Insertion into Metal-Ligand Bonds
generated by pulse radiolysis. In the presence of O2 the methylperoxide species [ N i ( ~ y c l a m ) ( H ~ 0 ) 0 0 C+, H 22, ~ ] ~forms24.
eo0 -
When the acyl-Pd complex 23 is exposed to O2 in the presence of excess Ph3P, an 0 atom inserts into the metal-carbon bondz5. 6
0
H2N-Pd-PPh3
I
PPh3 23
l-
0,
n OPPh,
1 1
1-
H2N-Pd-PPh3
PPh,
PPh3
In the absence of phosphine, a carboxylate-bridged dimer forms.
l+
Q-$ 0
2
H2N -Pd -PPh3 PPh3
H2N-Pd-PPh3
I
PPh3 23
OPPh,
(W. S. DURFEE) 1. T. V. Lubben, P. T. Wolczanski, J. Am. Chem. Soc., 107; 701 (1985). 2. T. V. Lubben, P. T. Wolczanski, J. Am. Chem. Soc., 109, 424 (1987). 3. P. T. Wolczanski, Polyhedron, 14, 3335 (1995). 4. 7. F. Blackburn, J. A. Labinger, J. Schwartz, Tetrahedron Lett., 3401 (1975). 5. J. A. Labinger, D. W. Hart, W. F. Seibert, 111, J. Schwartz, J. Am. Chem. Soc., 97, 3851 (1975). 6. R. Wang, K. Folting, J. C. Huffman, L. R. Chamberlain, I. P. Rothwell, Inorg. Chirn. Acta, 120, 8 1 (1986). 7 . F. Bottomley, C. P. Magill, P. S. White, J. Am. Chem. Soc., 111, 3070 (1989).
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 63 3.8.2.2 From Water 3.8.2.2.1 By Substitution of Transition and Inner Transition Metal Ligand Bonds 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25.
F. Bottomley, C. P. Magill, B. Zhao, Organometallics, 10, 1946 (1991). M. D. Curtis, K. R. Han, Inorg. Chem., 24, 378 (1985). F. Bottomley, J. Chen, Organometallics, 11: 3404 (1992). V. Riera, M. A. Ruiz, F, Villafafie, C. Bois, Y. Jeannin, Organometallics, 12, 124 (1993). B. Klingert, A. L. Rheingold, H. Werner, Inorg. Chem., 27, 1354 (1988). R. D. Arasasingham, A. L. Balch, C. R. Cornman, L. Latos-Grazynski, J. Am. Chem. Soc., 111, 4357 (1989). R. D. Arasasingham, A. L. Balch, R. L. Hart, L. Latos-Grazynski,J. Am. Chem. Soc., 112, 7566 (1990). S. Derenne, A. Gaudemer, M. D. Johnson, J . Organomet. Chem., 322, 229 (1987). F. R. Jensen, R. C. Kiskis, J. Am. Chem. Soc., 97, 5825 (1975). B. D. Gupta, M. Roy, I. Das, J . Organomet. Chem., 397, 219 (1990). J. Denian, A. Gaudemer, J . Organomet. Chem., 191, C1 (1980). A. E. Martell, A. K. Basak, C. J. Raleigh, Pure Appl. Chem., 60, 1325 (1988). P. J. Toscano, L. G. Marzilli, Prog. Inorg. Chem., 31, 105 (1984). M. J. Kendrick, W. Al-Akhdar, Inorg. Chem., 26, 3971 (1987). V. W. Day, W. G. Klemperer, S. P. Lockledge, D. J. Main, J ; Am. Chem. Soc., 112, 2031 (1990). M. Aresta, C. F. Nobile, J. Chem. Soc., Dalton Trans., 708 (1977). A. Sauer, H. Cohen, D. Meyerstein, I m r g . Chem., 27, 4578 (1988). J. Vincente, J.-A. Abad, A. D. Frankland, M.-C. Ramirez de Arellano, J . Chem. Soc., Chern. Commun.,959 (1997).
3.8.2.2From Water 3.8.2.2.1 By Substitution of Transition and Inner Transition Metal Ligand Bonds
Substitution reactions carried out in aqueous media yield the intermediate aquo complex. Thus the following aquation or acid hydrolysis reaction [MX5Y]"+
+ H 2 0 G [MX5(H20)]('+"' + Y -
(a)
is of prime importance in the study of aqueous media substitution reactions. Reactions of inert d3Cr3t ions and d6C03' ions occur slowly enough to permit easy measurement of reaction rates; consequently enormous amounts of information are available on the substitution reactions of these ions','. The first-stage aquation of [Co(NH3)4C12It proceeds at a much faster rate than that of [ C O ( N H ~ ) ~'Cindicating ~]~ that the substitution occurs via a dissociative mechanism; the higher positive charge on the latter species makes the Co-C1 bond cleavage more difficult3. Similarly, aquation of [RuC16I3- to [ R U C I ~ ( H ~ O ) ]takes ~ - only seconds, whereas the half-reaction for conversion of [RuC1(H20)5I2' into [ R u ( H z O ) ~ ] ~takes ' about a year4. As expected for a dissociative process, there is an increase in the rate of aquation of [Co(LL)2C12]+ (where LL represents a bidentate bulky ligand derived from H2NCH2CH2NHz),proceeding as follows:
+
[ C O ( L L ) ~ C I ~ ] H2O
+ [ C O ( L L ) ~ C ~ ( H Z O+) ] C1~
(b)
The bulk of the ligand is so much greater that the complex with the ligand, H2NC(Me2)C(Me2)NH2aquates instantaneously5. Rate of aquation of complexes [M(NH3)5YI2' (M = Co or Cr) to form [M(NH3)5(Hz0)l3+also depends on the leaving group Y - , and follows the order6: [HC03]- > [NO,]- > I - > Br- > C1- > [S04l2-
> F- > [CH3C00]- > [NCSl- > " 0 2 1 -
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 63 3.8.2.2 From Water 3.8.2.2.1 By Substitution of Transition and Inner Transition Metal Ligand Bonds 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25.
F. Bottomley, C. P. Magill, B. Zhao, Organometallics, 10, 1946 (1991). M. D. Curtis, K. R. Han, Inorg. Chem., 24, 378 (1985). F. Bottomley, J. Chen, Organometallics, 11: 3404 (1992). V. Riera, M. A. Ruiz, F, Villafafie, C. Bois, Y. Jeannin, Organometallics, 12, 124 (1993). B. Klingert, A. L. Rheingold, H. Werner, Inorg. Chem., 27, 1354 (1988). R. D. Arasasingham, A. L. Balch, C. R. Cornman, L. Latos-Grazynski, J. Am. Chem. Soc., 111, 4357 (1989). R. D. Arasasingham, A. L. Balch, R. L. Hart, L. Latos-Grazynski,J. Am. Chem. Soc., 112, 7566 (1990). S. Derenne, A. Gaudemer, M. D. Johnson, J . Organomet. Chem., 322, 229 (1987). F. R. Jensen, R. C. Kiskis, J. Am. Chem. Soc., 97, 5825 (1975). B. D. Gupta, M. Roy, I. Das, J . Organomet. Chem., 397, 219 (1990). J. Denian, A. Gaudemer, J . Organomet. Chem., 191, C1 (1980). A. E. Martell, A. K. Basak, C. J. Raleigh, Pure Appl. Chem., 60, 1325 (1988). P. J. Toscano, L. G. Marzilli, Prog. Inorg. Chem., 31, 105 (1984). M. J. Kendrick, W. Al-Akhdar, Inorg. Chem., 26, 3971 (1987). V. W. Day, W. G. Klemperer, S. P. Lockledge, D. J. Main, J ; Am. Chem. Soc., 112, 2031 (1990). M. Aresta, C. F. Nobile, J. Chem. Soc., Dalton Trans., 708 (1977). A. Sauer, H. Cohen, D. Meyerstein, I m r g . Chem., 27, 4578 (1988). J. Vincente, J.-A. Abad, A. D. Frankland, M.-C. Ramirez de Arellano, J . Chem. Soc., Chern. Commun.,959 (1997).
3.8.2.2From Water 3.8.2.2.1 By Substitution of Transition and Inner Transition Metal Ligand Bonds
Substitution reactions carried out in aqueous media yield the intermediate aquo complex. Thus the following aquation or acid hydrolysis reaction [MX5Y]"+
+ H 2 0 G [MX5(H20)]('+"' + Y -
(a)
is of prime importance in the study of aqueous media substitution reactions. Reactions of inert d3Cr3t ions and d6C03' ions occur slowly enough to permit easy measurement of reaction rates; consequently enormous amounts of information are available on the substitution reactions of these ions','. The first-stage aquation of [Co(NH3)4C12It proceeds at a much faster rate than that of [ C O ( N H ~ ) ~'Cindicating ~]~ that the substitution occurs via a dissociative mechanism; the higher positive charge on the latter species makes the Co-C1 bond cleavage more difficult3. Similarly, aquation of [RuC16I3- to [ R U C I ~ ( H ~ O ) ]takes ~ - only seconds, whereas the half-reaction for conversion of [RuC1(H20)5I2' into [ R u ( H z O ) ~ ] ~takes ' about a year4. As expected for a dissociative process, there is an increase in the rate of aquation of [Co(LL)2C12]+ (where LL represents a bidentate bulky ligand derived from H2NCH2CH2NHz),proceeding as follows:
+
[ C O ( L L ) ~ C I ~ ] H2O
+ [ C O ( L L ) ~ C ~ ( H Z O+) ] C1~
(b)
The bulk of the ligand is so much greater that the complex with the ligand, H2NC(Me2)C(Me2)NH2aquates instantaneously5. Rate of aquation of complexes [M(NH3)5YI2' (M = Co or Cr) to form [M(NH3)5(Hz0)l3+also depends on the leaving group Y - , and follows the order6: [HC03]- > [NO,]- > I - > Br- > C1- > [S04l2-
> F- > [CH3C00]- > [NCSl- > " 0 2 1 -
64 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.2 From Water 3.8.2.2.2 By Hydrolysis of Transition and Inner Transition Metal-Ligand Bonds
Aquation of cis-[Co(en)~AXl' (A = C1-, Br-, [OH]- and [NCSl-; X = C1- and Br-) complexes forms the ~is-[Co(en)zA(H20)]'~ by an s N 1 mechanism through a square-pyramidal intermediate. However, aquation of the corresponding transderivatives proceeds with a change of configuration giving ~is-[Co(en)zA(HzO)]~ ' complexes by an s N 1 mechanism through a trigonal-bipyramid intermediate's',*. In aqueous solutions, the [ M o C ~ ~ ] ion ~ - is readily aquated; dissolution of K3 [MoC16]' in aqueous CF3S03H or P - C H ~ C ~ H ~ Syields O ~ H [Mo(H20)6I3+. No aquo ions of W in any oxidation state are known4. Unlike [ C o ( H ~ 0 ) 6 ] ~ the + , yellow complex ion [Rh(H20)6]3' is stable and can be obtained by repeated evaporation of HC104 solutions of RhC13. 3H20''. (R. C.MEHROTRA, B. S. SARASWAT) F. Basolo, R. G. Pearson, Mechanism of Inorganic Reactions, Wiley, New York, 1958. D. Nicholls, Complexes and First Row Transition Elements, Macmillan, London, 1979. R. G. Pearson, C. R. Boston, F. Basolo, J. Phys. Chem., 59, 304 (1995). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. R. G. Pearson, C. R. Boston, F. Basolo, J . Am. Chern. Soc., 75, 3089 (1953); F. Basolo, R. G. Pearson, A d a Inorg. Chem. Radiochem., 3, 1 (1961). 6. A. W. Adamson, R. G. Wilkins, J . Am. Chem. Soc., 76, 3379 (1954); D. W. Hoppenjans, J. B. Hunt, C. R. Gregoire, Inorg. Chem., 7, 2506 (1968). 7. F. E. Baldwin, M. L. Tobe, J. Chem. Soc., 4275 (1960). 8. S. C. Chan, M. L. Tobe, J . Chem. Soc., 5700 (1963). 9. A. R. Bowen, H. Taube, J . Am. Chem. Soc., 93,3287 (1971); Y . Sasaki, A. G. Sykes, J . Chem. Soc., Chem. Commun., 767 (1973). 10. K. E. Hyde, H. Kelm, D. A. Palmer, Inorg. Chem., 17, 1647 (1978). 1. 2. 3. 4. 5.
3.8.2.2.2 By Hydrolysis of Transition and Inner Transition Metal-Ligand Bonds
Transition metal ions in aqueous solution yield hexaquo ions, [M(H20)6]" act as proton donors owing to hydrolysis: [M(H20)6]"'
+ H z O e [M(Hz0)5]'"-''' + H 3 0 '
which (a)
Their acidity or ability to act as proton donors varies widely and depends on the charge-to-size ratio of the ion, Whereas dipositive transition metal ions (e.g., Mn", Fe", Co", Ni") are only weakly acidic, the tripositive ions are strong acids. Species of types [Ti(H20)6]4+ and [ ~ ( H z O ) ~ ]of~ 'smaller M4' ions are far too acidic to exist, and only hydrolyzed species form in aqueous solution. For Ti4' in dilute HC104, the hydrolytic equilibrium lies in the region':
+
[ T i ( H 2 0 ) 4 ( 0 H ) ~ ] ~ ' HzOe [Ti(Hz0)3(0H)~]'
+ H30'
(b)
whereas for V4+, [VO(HZO)S]'~is the main species in solution'. The Zr4' aqueous chemistry is more extensive because hydrolysis is less complete. The state of Zr4 ' in aqueous solution is not simple. There is no indication of Zr4' or Zr0" ions. In strong acid solutions (pH < l), [ZrOHl3' and [HfOHI3+ ions exist3. The Th4+ ion is even more resistant to hydrolysis and undergoes extensive hydrolysis in aqueous solution only at p H higher than ca. 3; the species formed are complex and dependent on concentration and p H of solution and nature of anions. Binuclear species with hydroxo bridges are characterized, and there are more complicated polymers4.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
64 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.2 From Water 3.8.2.2.2 By Hydrolysis of Transition and Inner Transition Metal-Ligand Bonds
Aquation of cis-[Co(en)~AXl' (A = C1-, Br-, [OH]- and [NCSl-; X = C1- and Br-) complexes forms the ~is-[Co(en)zA(H20)]'~ by an s N 1 mechanism through a square-pyramidal intermediate. However, aquation of the corresponding transderivatives proceeds with a change of configuration giving ~is-[Co(en)zA(HzO)]~ ' complexes by an s N 1 mechanism through a trigonal-bipyramid intermediate's',*. In aqueous solutions, the [ M o C ~ ~ ] ion ~ - is readily aquated; dissolution of K3 [MoC16]' in aqueous CF3S03H or P - C H ~ C ~ H ~ Syields O ~ H [Mo(H20)6I3+. No aquo ions of W in any oxidation state are known4. Unlike [ C o ( H ~ 0 ) 6 ] ~ the + , yellow complex ion [Rh(H20)6]3' is stable and can be obtained by repeated evaporation of HC104 solutions of RhC13. 3H20''. (R. C.MEHROTRA, B. S. SARASWAT) F. Basolo, R. G. Pearson, Mechanism of Inorganic Reactions, Wiley, New York, 1958. D. Nicholls, Complexes and First Row Transition Elements, Macmillan, London, 1979. R. G. Pearson, C. R. Boston, F. Basolo, J. Phys. Chem., 59, 304 (1995). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. R. G. Pearson, C. R. Boston, F. Basolo, J . Am. Chern. Soc., 75, 3089 (1953); F. Basolo, R. G. Pearson, A d a Inorg. Chem. Radiochem., 3, 1 (1961). 6. A. W. Adamson, R. G. Wilkins, J . Am. Chem. Soc., 76, 3379 (1954); D. W. Hoppenjans, J. B. Hunt, C. R. Gregoire, Inorg. Chem., 7, 2506 (1968). 7. F. E. Baldwin, M. L. Tobe, J. Chem. Soc., 4275 (1960). 8. S. C. Chan, M. L. Tobe, J . Chem. Soc., 5700 (1963). 9. A. R. Bowen, H. Taube, J . Am. Chem. Soc., 93,3287 (1971); Y . Sasaki, A. G. Sykes, J . Chem. Soc., Chem. Commun., 767 (1973). 10. K. E. Hyde, H. Kelm, D. A. Palmer, Inorg. Chem., 17, 1647 (1978). 1. 2. 3. 4. 5.
3.8.2.2.2 By Hydrolysis of Transition and Inner Transition Metal-Ligand Bonds
Transition metal ions in aqueous solution yield hexaquo ions, [M(H20)6]" act as proton donors owing to hydrolysis: [M(H20)6]"'
+ H z O e [M(Hz0)5]'"-''' + H 3 0 '
which (a)
Their acidity or ability to act as proton donors varies widely and depends on the charge-to-size ratio of the ion, Whereas dipositive transition metal ions (e.g., Mn", Fe", Co", Ni") are only weakly acidic, the tripositive ions are strong acids. Species of types [Ti(H20)6]4+ and [ ~ ( H z O ) ~ ]of~ 'smaller M4' ions are far too acidic to exist, and only hydrolyzed species form in aqueous solution. For Ti4' in dilute HC104, the hydrolytic equilibrium lies in the region':
+
[ T i ( H 2 0 ) 4 ( 0 H ) ~ ] ~ ' HzOe [Ti(Hz0)3(0H)~]'
+ H30'
(b)
whereas for V4+, [VO(HZO)S]'~is the main species in solution'. The Zr4' aqueous chemistry is more extensive because hydrolysis is less complete. The state of Zr4 ' in aqueous solution is not simple. There is no indication of Zr4' or Zr0" ions. In strong acid solutions (pH < l), [ZrOHl3' and [HfOHI3+ ions exist3. The Th4+ ion is even more resistant to hydrolysis and undergoes extensive hydrolysis in aqueous solution only at p H higher than ca. 3; the species formed are complex and dependent on concentration and p H of solution and nature of anions. Binuclear species with hydroxo bridges are characterized, and there are more complicated polymers4.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.3 From Hydrogen Peroxide 3.8.2.3.1 By Oxidation of Transition and Inner Transition Metal Elements
65
Although the aquo ions [M(H20)6]3+ (M = Ti, V, Cr, Mn, Fe, etc.) exist in complexing acids, these too are strong acids and are hydrolyzed in H 2 0 to give hydroxo species2:
+
+ [ ~ ( H Z O ) ~+] ~H20 ' [V(Hz0)50H]2C + H 3 0 + , [Cr(Hz0)6I3+ + H z O + [ C ~ ( H ~ O ) ~ O H+] ~H+3 0 + , [Mn(H20)6I3+ + H ~ O ~ [ M ~ ( H Z O ) ~ O + H 3] 0~++, [Fe(H20)6I3+ + HzO$[Fe(HzO)50H]*+ + H 3 0 + , [Ti(HzO)6]3+ H20* [Ti(H20)50H]2+ H 3 0 + ,
pK1 = 1.4
(4
pK1 = 2.9
(d)
pK1 = 1.6
(el
pK1 = 0.9
(f)
pK1 = 3.05
(g)
The aquo ions [Ln(Hz0),J3+ are hydrolyzed in H z 0 5 : [Ln(H20),J3+
+ H 2 0 e [ L n ( H 2 0 ) , - 1 0 H ] ~ ++ H30'
(h)
The tendency to hydrolysis increases with increasing atomic number, as expected from the contraction in radii. Yttrium gives predominantly [YOHI2+,but also [Yz(OH)Z]~+ ions. For Ce3+, however, only 1% of the metal ion is hydrolyzed without forming a precipitate. The main equilibrium is:
+
3Ce3+(aq) 1 0 H z O e [Ce3(OH)5(aq)I4++ 5H30+
(i)
Aqueous solutions of U salts are acidic owing to hydrolysis and the acidity increases in the following order: U 3 + < [UOZ]" < U 4 + .The main hydrolyzed species of UO:' at 25°C are [UOzOH]', [ ( U O Z ) ~ ( O H ) Z ]and ~ + ,[(UO2)3(OH)s]+. The system is complex and the species present depend on the medium5. The U4+ ion is only slightly hydrolyzed in molar acid solutions6:
+
U4+(aq) 2H20$[UOHI3+(aq)
+ H30+,
pK = 1.56
( j1
( R. C.MEHROTRA, 6.S. SARASWAT) J. D. Ellis, A. G. Sykes, J . Chem. Soc., Dalton Trans., 537 (1973). D. Nicholls, Complexes and First Row Transition Elements, Macmillan, London, 1979. B. Noren, Acta Chem. Scand., 27A, 1369 (1973). M. Magini, A. Carbini, G. Scibona, G. Johnansson, M. Sandstrom, Acta Chem. Scand., 30A, 437 (1976). 5. F. A. Cotton, G. Wilkinson, AdGanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. 6. R. N. Sylva, M. R. Davidson, J . Chem. Soc., Dalton Trans., 465 (1979).
1. 2. 3. 4.
3.8.2.3 From Hydrogen Peroxide 3.8.2.3.1 By Oxidation of Transition and Inner Transition Metal Elements and Their Complexes
There are few reports of neutral H202 reactions with metals, other than the catalytic effect of the latter on the decomposition of H202. Metals known to be virtually unaffected by 30% H202 include Y, Ti, Zr, Hf, Nb, and Ta. Cobalt is oxidized to CO(OH)3,Mo and W to the trioxides, and Re to HRe04'. Most of the lanthanide metals, with the exception of Gd, Dy, and Ho, are surface-oxidized by H202 at 40"C2. Ammonical solutions of Co2+ salts, presumably containing [ C O ( N H ~ +, ) ~ are ]~ . ~Metal )~] oxidized by H202 to the green paramagentic [ ( N H ~ ) ~ C O O ~ C O ( 5Nf 'H
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.3 From Hydrogen Peroxide 3.8.2.3.1 By Oxidation of Transition and Inner Transition Metal Elements
65
Although the aquo ions [M(H20)6]3+ (M = Ti, V, Cr, Mn, Fe, etc.) exist in complexing acids, these too are strong acids and are hydrolyzed in H 2 0 to give hydroxo species2:
+
+ [ ~ ( H Z O ) ~+] ~H20 ' [V(Hz0)50H]2C + H 3 0 + , [Cr(Hz0)6I3+ + H z O + [ C ~ ( H ~ O ) ~ O H+] ~H+3 0 + , [Mn(H20)6I3+ + H ~ O ~ [ M ~ ( H Z O ) ~ O + H 3] 0~++, [Fe(H20)6I3+ + HzO$[Fe(HzO)50H]*+ + H 3 0 + , [Ti(HzO)6]3+ H20* [Ti(H20)50H]2+ H 3 0 + ,
pK1 = 1.4
(4
pK1 = 2.9
(d)
pK1 = 1.6
(el
pK1 = 0.9
(f)
pK1 = 3.05
(g)
The aquo ions [Ln(Hz0),J3+ are hydrolyzed in H z 0 5 : [Ln(H20),J3+
+ H 2 0 e [ L n ( H 2 0 ) , - 1 0 H ] ~ ++ H30'
(h)
The tendency to hydrolysis increases with increasing atomic number, as expected from the contraction in radii. Yttrium gives predominantly [YOHI2+,but also [Yz(OH)Z]~+ ions. For Ce3+, however, only 1% of the metal ion is hydrolyzed without forming a precipitate. The main equilibrium is:
+
3Ce3+(aq) 1 0 H z O e [Ce3(OH)5(aq)I4++ 5H30+
(i)
Aqueous solutions of U salts are acidic owing to hydrolysis and the acidity increases in the following order: U 3 + < [UOZ]" < U 4 + .The main hydrolyzed species of UO:' at 25°C are [UOzOH]', [ ( U O Z ) ~ ( O H ) Z ]and ~ + ,[(UO2)3(OH)s]+. The system is complex and the species present depend on the medium5. The U4+ ion is only slightly hydrolyzed in molar acid solutions6:
+
U4+(aq) 2H20$[UOHI3+(aq)
+ H30+,
pK = 1.56
( j1
( R. C.MEHROTRA, 6.S. SARASWAT) J. D. Ellis, A. G. Sykes, J . Chem. Soc., Dalton Trans., 537 (1973). D. Nicholls, Complexes and First Row Transition Elements, Macmillan, London, 1979. B. Noren, Acta Chem. Scand., 27A, 1369 (1973). M. Magini, A. Carbini, G. Scibona, G. Johnansson, M. Sandstrom, Acta Chem. Scand., 30A, 437 (1976). 5. F. A. Cotton, G. Wilkinson, AdGanced Inorganic Chemistry, 5th ed., Wiley, New York, 1988. 6. R. N. Sylva, M. R. Davidson, J . Chem. Soc., Dalton Trans., 465 (1979).
1. 2. 3. 4.
3.8.2.3 From Hydrogen Peroxide 3.8.2.3.1 By Oxidation of Transition and Inner Transition Metal Elements and Their Complexes
There are few reports of neutral H202 reactions with metals, other than the catalytic effect of the latter on the decomposition of H202. Metals known to be virtually unaffected by 30% H202 include Y, Ti, Zr, Hf, Nb, and Ta. Cobalt is oxidized to CO(OH)3,Mo and W to the trioxides, and Re to HRe04'. Most of the lanthanide metals, with the exception of Gd, Dy, and Ho, are surface-oxidized by H202 at 40"C2. Ammonical solutions of Co2+ salts, presumably containing [ C O ( N H ~ +, ) ~ are ]~ . ~Metal )~] oxidized by H202 to the green paramagentic [ ( N H ~ ) ~ C O O ~ C O ( 5Nf 'H
66
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.4 From Alcohols and Phenols 3.8.2.4.1 Substitution of Transition and Inner Transition Metal-Ligand Bonds
phthalocyanines of V3+,Cr3+,M4', C o 2 + ,N i 2 + ,Rh3+,Ru3+,P d Z + Os4+, , and Ir3+ in 17 M H 2 S 0 4 are destructively oxidized by H202, yielding the metal aquo or sulfato complex, or oxide4. (M. T. POPE)
1. 2. 3. 4.
N. P. Johnson, C. J. L. Lock, G. Wilkinson, Inorg. Synth., 9, 145 (1967). K. Lee, N. D. Green, Corrosion, 20, 145 (1964). K. Gleu, K. Rehn, Z. Anorg. Allgm. Chem., 237, 79 (1938). B. D. Berezin, G. V. Sennikova, Kinet. Catal. (Eng. transl.), 9, 437 (1968).
3.8.2.3.2 By Oxidation of a Ligand Coordinated to a Transition and Inner Transition Metal Complex (Insertion Reaction)
No reactions of this category appear to have been systematically investigated.
(M.T. POPE) 3.8.2.3.3 By Homolytic Transition and Inner Transition Metal-Ligand Substitution Reactions
No reactions of this category appear to have been investigated, but see 3.8.2.9.1for reactions of Oi-. (M. T . POPE)
3.8.2.4 From Alcohols and Phenols 3.8.2.4.1 By Substitution of Transition and Inner Transition Metal- Ligand Bonds
In anhydrous MeOH and EtOH, Tic13 exits mainly as [Ti(ROH)6I3+ and [TiC12(ROH)2If ions'. Reactions of ROH (R = Me, i-Pr, s-Bu, and C6Hll) with vc13 form [V(ROH)4C12]C1, but those of R'OH (R' = Et, n-Pr, and n-Bu) yield simple adducts, vc13.3R'OH2. Reaction of CrC13 with MeOH gives trans[Cr(MeOH)4C12]C13. Reactions of CrC13 3THF with excess alcohols under strictly anhydrous conditions also form alcoholate complexes [Cr(ROH)4C12]Cl (R = Me, Et, and i-Pr) and [CrC13 3ROH1 (R = n-Bu and n-Hex), depending on the conditions4. The alcoholates also undergo transalcoholysis: '
[Cr(ROH)4C12]Cl
+ 4R'OH
(R = Me, R'
=
-
[Cr(R'OH)4C12]C1
i-Pr; R
= Et
+ 4ROH
(a)
and i-Pr, R' = Me)
Similarly, the methanolate NiClz MeOH undergoes transalcoholysis to yield the alocholates of branched alcohols, which cannot be prepared by the direct reaction of NiClzwith R'OH5,? NiClz. MeOH
+ R'OH
-
NiC12. R O H
+ MeOH
(b)
(R' = i-Pr, t-Bu, and t-Am) The alcoholate CoC12.2EtOH is prepared by the direct reaction of EtOH with coc12. 6 H 2 0 in refluxing C6H6 by removing H 2 0 azeotropically7. (R. C. MEHROTRA, B. S. SARASWAT)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
66
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.4 From Alcohols and Phenols 3.8.2.4.1 Substitution of Transition and Inner Transition Metal-Ligand Bonds
phthalocyanines of V3+,Cr3+,M4', C o 2 + ,N i 2 + ,Rh3+,Ru3+,P d Z + Os4+, , and Ir3+ in 17 M H 2 S 0 4 are destructively oxidized by H202, yielding the metal aquo or sulfato complex, or oxide4. (M. T. POPE)
1. 2. 3. 4.
N. P. Johnson, C. J. L. Lock, G. Wilkinson, Inorg. Synth., 9, 145 (1967). K. Lee, N. D. Green, Corrosion, 20, 145 (1964). K. Gleu, K. Rehn, Z. Anorg. Allgm. Chem., 237, 79 (1938). B. D. Berezin, G. V. Sennikova, Kinet. Catal. (Eng. transl.), 9, 437 (1968).
3.8.2.3.2 By Oxidation of a Ligand Coordinated to a Transition and Inner Transition Metal Complex (Insertion Reaction)
No reactions of this category appear to have been systematically investigated.
(M.T. POPE) 3.8.2.3.3 By Homolytic Transition and Inner Transition Metal-Ligand Substitution Reactions
No reactions of this category appear to have been investigated, but see 3.8.2.9.1for reactions of Oi-. (M. T . POPE)
3.8.2.4 From Alcohols and Phenols 3.8.2.4.1 By Substitution of Transition and Inner Transition Metal- Ligand Bonds
In anhydrous MeOH and EtOH, Tic13 exits mainly as [Ti(ROH)6I3+ and [TiC12(ROH)2If ions'. Reactions of ROH (R = Me, i-Pr, s-Bu, and C6Hll) with vc13 form [V(ROH)4C12]C1, but those of R'OH (R' = Et, n-Pr, and n-Bu) yield simple adducts, vc13.3R'OH2. Reaction of CrC13 with MeOH gives trans[Cr(MeOH)4C12]C13. Reactions of CrC13 3THF with excess alcohols under strictly anhydrous conditions also form alcoholate complexes [Cr(ROH)4C12]Cl (R = Me, Et, and i-Pr) and [CrC13 3ROH1 (R = n-Bu and n-Hex), depending on the conditions4. The alcoholates also undergo transalcoholysis: '
[Cr(ROH)4C12]Cl
+ 4R'OH
(R = Me, R'
=
-
[Cr(R'OH)4C12]C1
i-Pr; R
= Et
+ 4ROH
(a)
and i-Pr, R' = Me)
Similarly, the methanolate NiClz MeOH undergoes transalcoholysis to yield the alocholates of branched alcohols, which cannot be prepared by the direct reaction of NiClzwith R'OH5,? NiClz. MeOH
+ R'OH
-
NiC12. R O H
+ MeOH
(b)
(R' = i-Pr, t-Bu, and t-Am) The alcoholate CoC12.2EtOH is prepared by the direct reaction of EtOH with coc12. 6 H 2 0 in refluxing C6H6 by removing H 2 0 azeotropically7. (R. C. MEHROTRA, B. S. SARASWAT)
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 67 3.8.2.4 From Alcohols and Phenols 3.8.2.4.2 By Alcoholysis of Transition and Inner Transition Metal-Ligand Bonds ~
~~
1. B. Pittel, W. H. E. Schwarz, Z. Anorg. Allg. Chem., 396, 152 (1973). 2. A. T. Casey, R. J. H. Clark, Inorg. Chem., 8, 1216 (1969); Y. Dhoi, M. Tsutsui, J . Am. Chem. Soc., 100, 324 (1978). 3. K. I. Hardcastle, D. 0. Skovlin, A. H. Eidaward, J . Chem. Soc., Chem. Commun., 190 (1975). 4. K. N. Mahendra, Ph.D. thesis, University of Delhi, Delhi, 1979. 5. B. P. Baranwal, R. C. Mehrotra, 2. Anorg. Allg. Chem., 443, 284 (1978). 6. R. C. Mehrotra, in Coordination Chemistry-2l, IUPAC, J. P. Laurent, ed., Pergamon Press, Oxford, 1981, p. 113. 7. J. V. Singh, N. C. Jain, R. C. Mehrotra, Z . Naturforsch., Teil B, 155 (1980).
3.8.2.4.2 By Alcoholysis of Transition and Inner Transition Metal-Ligand Bonds
Alcohols react with transition metal halides, replacing metal-halogen bonds with alkoxy groups to varying extents', e g : Tic14 + 3EtOHVC14 + 4EtOH-
+ 2HC1 VC12(OEt)2 2EtOH + 2HC1 TiC12(0Et),.EtOH
(a) (b)
Alcoholysis of NbC15, TaC13, MoC15, and WCI5, ~ i m i l a r l y ~yields , ~ , only the partially substituted Nb(OR)3C12, Ta(OR)3C12, Mo(OMe)2C13, and W(OMe)2CL . 3MeOH4 derivatives, respectively. Although WC16 reacts with PhOH at 180-200°C during 10-12 h to yield W(OPh)65,synthesis of alkoxides of several transition and inner transition metals is achieved by alcoholysis of metal chlorides in an inert solvent like benzene in the presence of bases like NH3, C5HjN, or Et3N. The alkoxides of Ti(IV), Zr(IV), Hf(IV), V(IV), Nb(V), Ta(V), Ce(IV), U(IV), Th(IV), and Pu(1V) are prepared by bubbling dry NH3 gas through a benzene solution of metal chloride and excess alcohol'. Reactions of MnBr(CO)5 with ROH(R = Et, i-Pr, and n-Bu) in presence of Et3N yield trimeric Mn alkoxides6: 3MnBr(C0)j + 3ROH
+ 3Et,N-
[Mn(OR)(CO),],
+ 6CO + 3Et3NHBr
(c)
Phenolysis of Et,Ni(bipy) yields the monophenoxy derivative, E t N i O P h ( b i ~ y ) ~ . However, reactions of EtzFe(bipy), with ROH (R = Me, Et, i-Pr and Bz) and p-XC6H40H (X = H, Me, Ph, C1, CN, and NOz) cleave both Fe-C bonds, yielding the corresponding dialkoxy or diaryloxy derivatives, (RO),Fe(bipy), and ( p XC6H40)2Fe(bipy),, respectively'. Alcoholysis of cylopentadienyl complexes of Ti(IV), MoO(IV),and WO(1V) leads to partial substitution of cyclopentadienyl by alkoxy groupsg: Cp2MClz
+ EtOH(M
= Ti,
CpM(OEt)C12
+ C5H6
(dl
MOO, and WO)
Dicyclopentadienylchromium reacts with primary and secondary alcohols to yield polymeric alkoxides, [Cr(OR),], (R = Me, Et, and i-Pr). However, with t-BuOH the dimeric product [CpCr(OBu-t)lz forms". Reactions of U (y3-C3Hj)4with ROH (R = Et, i-Pr, and t-Bu) in EtzO or n-C6HI4 at - 30'C in 1 :2 molar ratio yield the dialkoxy derivatives: U(q3-C3H5)4 + 2ROH-
U(y3-C3H5)2(OR)2 + 2C3H6
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 67 3.8.2.4 From Alcohols and Phenols 3.8.2.4.2 By Alcoholysis of Transition and Inner Transition Metal-Ligand Bonds ~
~~
1. B. Pittel, W. H. E. Schwarz, Z. Anorg. Allg. Chem., 396, 152 (1973). 2. A. T. Casey, R. J. H. Clark, Inorg. Chem., 8, 1216 (1969); Y. Dhoi, M. Tsutsui, J . Am. Chem. Soc., 100, 324 (1978). 3. K. I. Hardcastle, D. 0. Skovlin, A. H. Eidaward, J . Chem. Soc., Chem. Commun., 190 (1975). 4. K. N. Mahendra, Ph.D. thesis, University of Delhi, Delhi, 1979. 5. B. P. Baranwal, R. C. Mehrotra, 2. Anorg. Allg. Chem., 443, 284 (1978). 6. R. C. Mehrotra, in Coordination Chemistry-2l, IUPAC, J. P. Laurent, ed., Pergamon Press, Oxford, 1981, p. 113. 7. J. V. Singh, N. C. Jain, R. C. Mehrotra, Z . Naturforsch., Teil B, 155 (1980).
3.8.2.4.2 By Alcoholysis of Transition and Inner Transition Metal-Ligand Bonds
Alcohols react with transition metal halides, replacing metal-halogen bonds with alkoxy groups to varying extents', e g : Tic14 + 3EtOHVC14 + 4EtOH-
+ 2HC1 VC12(OEt)2 2EtOH + 2HC1 TiC12(0Et),.EtOH
(a) (b)
Alcoholysis of NbC15, TaC13, MoC15, and WCI5, ~ i m i l a r l y ~yields , ~ , only the partially substituted Nb(OR)3C12, Ta(OR)3C12, Mo(OMe)2C13, and W(OMe)2CL . 3MeOH4 derivatives, respectively. Although WC16 reacts with PhOH at 180-200°C during 10-12 h to yield W(OPh)65,synthesis of alkoxides of several transition and inner transition metals is achieved by alcoholysis of metal chlorides in an inert solvent like benzene in the presence of bases like NH3, C5HjN, or Et3N. The alkoxides of Ti(IV), Zr(IV), Hf(IV), V(IV), Nb(V), Ta(V), Ce(IV), U(IV), Th(IV), and Pu(1V) are prepared by bubbling dry NH3 gas through a benzene solution of metal chloride and excess alcohol'. Reactions of MnBr(CO)5 with ROH(R = Et, i-Pr, and n-Bu) in presence of Et3N yield trimeric Mn alkoxides6: 3MnBr(C0)j + 3ROH
+ 3Et,N-
[Mn(OR)(CO),],
+ 6CO + 3Et3NHBr
(c)
Phenolysis of Et,Ni(bipy) yields the monophenoxy derivative, E t N i O P h ( b i ~ y ) ~ . However, reactions of EtzFe(bipy), with ROH (R = Me, Et, i-Pr and Bz) and p-XC6H40H (X = H, Me, Ph, C1, CN, and NOz) cleave both Fe-C bonds, yielding the corresponding dialkoxy or diaryloxy derivatives, (RO),Fe(bipy), and ( p XC6H40)2Fe(bipy),, respectively'. Alcoholysis of cylopentadienyl complexes of Ti(IV), MoO(IV),and WO(1V) leads to partial substitution of cyclopentadienyl by alkoxy groupsg: Cp2MClz
+ EtOH(M
= Ti,
CpM(OEt)C12
+ C5H6
(dl
MOO, and WO)
Dicyclopentadienylchromium reacts with primary and secondary alcohols to yield polymeric alkoxides, [Cr(OR),], (R = Me, Et, and i-Pr). However, with t-BuOH the dimeric product [CpCr(OBu-t)lz forms". Reactions of U (y3-C3Hj)4with ROH (R = Et, i-Pr, and t-Bu) in EtzO or n-C6HI4 at - 30'C in 1 :2 molar ratio yield the dialkoxy derivatives: U(q3-C3H5)4 + 2ROH-
U(y3-C3H5)2(OR)2 + 2C3H6
68 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond
3.8.2.4 From Alcohols and Phenols 3.8.2.4.2 By Alcoholysis of Transition and Inner Transition Metal-Ligand Bonds
However, reaction with excess alcohol in E t 2 0 at RT gives the tetraalkoxy derivatives, U(OR)41l . Reactions of dialkylmetal amides, M(NR2), [M = V(IV), Ti(IV), Zr(IV)], Cr(IV), U(IV), and Ta(IV)] with R’OH in hydrocarbon solvents cause their facile conversion to metal alkoxides’.’2: M(NR2),
+ nR’OH-
M(OR),
+ nR2NH
(f)
This alcoholysis is particularly useful for alkoxides that are inaccessible by other methods. Alkoxides of V(IV)I3, Mo(II)I4, and W(III)” are conveniently prepared by ) ~ ,W2(NMe2)6,respectively, e.g.: alcoholysis of V(NMe2)4,M o , ( N M ~ ~and V(NMe,),
+ 4ROH-
V(OR)4 + 4Me2NH
(g)
(R = i-Pr and t-Bu) Addition of MeOH to Cr(NO)(N-i-Pr2)3yields the highly polymeric Cr(OMe)3. However, i-PrOH gives only the dimer Cr,(NO)2(OPr-i)6, whereas the bulky t-BuOH forms the monomer Cr(NO)(N-i-Pr2)3 -x(OBu-t), (x = 1-3)16. Alcoholysis of Mn[N(SiMe3)2]2.L, (L = THF, py, or t-BuCN; n = 0, 1, or 2) in hydrocarbon solvents yields a series of Mn(I1) alk~xides’~: Mn[N(SiMe3)2]2‘L, [R
=
+ 2ROH-
Mn(OR),
+ 2(Me3Si),NH + nL
(h)
Me, Et, i-Pr, n-Bu, s-Bu, t-Bu, t-BuCH,,
Et3C, 2 , 6 - ( t - B ~ ) ~ C &and ~, 2,4,6-(t-B~)~C~H~] Sterically hindered (t-Bu),CHOH does not react with V(NEt2)4, Cr(NEt2)4, or Cr[N(SiMe3),13 even in boiling toluene, but does react with some bis derivatives in refluxing benezene, e.g.: Mn[N(SiMe3)2]2
+ 2(t-Bu),CHOH-
M[OCH(Bu-t),],
+ 2(Me3Si)2NH
(i)
(M = Cr’*, Mn”, and Co”) Alkane solutions of M O ~ ( N Mreact ~ ~ smoothly )~ with ROH [R = Me, Et, n-Pr, i-Pr, t-Bu, t-BuCH,, and Me2(Ph)C] yielding Mo(II1) alkoxides of empirical formula, M ~ ( O R )1,3 . 2 0 . 2 1 .
+
M O ~ ( N M ~ , 6ROH)~
+
~ M o ( O R ) ~6Me2NH
(j)
The ease of alcoholysis decreases so greatly with the condition of the alkyl group that even under refluxing conditions with Et3COH, only partial substitution occurs, yielding M O ~ ( O C E ~ ~ ) ~ ( N M ~ , ) ~ ~ ~ . Alcoholysis of M O ( N M ~similarly ~ ) ~ results in formation of Mo(1V) alkoxidesZ2: Mo(NMe& [R
=
+ 4ROH-
+
M o ( O R ) ~ 4Me2NH
(k)
Me, Et, i-Pr, t-Bu, and t-BuCH,]
Reaction of W2(NMez) with t-BuOH in hydrocarbons at RT yields the dimeric species W2(OBu-t),. However with less bulky alcohols, (e.g., MeOH, i-PrOH, and t-BuCH20H), the polynuclear species [W(OR),], f ~ r m ’ ~ , ~ ~ .
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 69 3.8.2.4 From Alcohols and Phenols 3.8.2.4.3 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
Alkane solutions of W(NMe2)6 react smoothly, but relatively slowly with ROH (R = Me, Et, n-Pr, i-Pr, and CH2=CHCHz)z4yielding alkoxides, W(OR)6: W(NMed4
+ 6ROH-
W(OR)6
+ 6MezNH
However, t-BuOH and t-BuCH,OH fail to react to any appreciable extent at RT. In refluxing C6H6 with r-BuOH, a slow reaction yields W O ( O B U - ~ ) ~ ~ ~ , ~ ~ . (R. C. MEHROTRA, 6.S. SARASWAT) D. C. Bradley, R. C. Mehrotra, D. P. Gaur, Metal Alkoxides,Academic Press, London, 1978. D. L. Kepert, T h e Early Transition Metals, Academic Press, London, 1972, p. 175 D. C. Bradley, R. K. Multani, W. Wardlaw, J . Chem. SOC.,4647 (1958). H. Funk, H. Naumann, 2. Anorg. Allg. Chem., 343 294 (1966). Yu. V. Basikhin, P. P. Rodionov, N. P. Sysoeva, K. P. Lel'kin, Khim. Promst., Ser: Reakt, Osobo Chist. Veshchestu., 11 (1979); Chem. Abstr., 91, 1 8 5 8 3 3 ~(1979). 6. E. W. Ebel, G. Farrow, I. D. H. Towle, J.Chem. Soc., Dalton Trans., 71 (1979). 7. G. Wilke, G. Hermann, Angew. Chem., lnt. Ed. Engl., 5, 581 (1966). 8. S . Komiya, S . Tane-ichi, A. Yamamoto, T. Yamamoto, Bull. Chem. Soc. Jpn., 53, 673 (1980). 9. P. C. Bharara, V. D. Gupta, R. C. Mehrotra, Orgnomet. Chem. Rev., 5, 259 (1977). 10. M. H. Chisholm, F. A. Cotton, M. W. Extine, D. C. Redeout, Inorg. Chem., 18, 120 (1979). 11. M. Brunelli, G. Perego, G. Lugli, A. Mazzei, J . Chem. Soc., Dalton Trans., 861 (1979). 12. M. F. Lappert, P. P. Power, A. R. Sanger, R. C. Srivastava, Metal and Metalloid Amides, Ellis Horwood, Chichester, 1980, p. 610. 13. I. M. Thomas, Can J . Chem., 39, 1386 (1961). 14. M. H. Chisholm, W. Reichert, J . Am. Chem. Soc., 96, 1249 (1974). 15. M. H. Chisholm, M. W. Extine, J . Am. Chem. Soc., 97, 5625 (1975). 16. D.C. Bradley, C. W. Newing, M. H. Chisholm, R. L. Kelly, D. A. Hatko, D. Little, F. A. Cotton, P. E. Fanwick, Inorg. Chem., 19, 3010 (1980). 17. B. Horvath, R. Moseler, E. G. Horvath, Z . Anorg. Allg. Chem., 449, 41 (1979). 18. B. Horvath, E. G. Horvath, 2. Anorg. Allg. Chem., 457, 51 (1979). 19. M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 1863 (1980). 20. M. H. Chisholm. F. A. Cotton, C. A. Murillo, Inorg. Chem., 16, 180 (1977). 21. M. H. Chisholm, W. W. Reichert, F. A. Cotton, C. A. Murillo, J . Am. Chem. Soc.,99,1652 (1977). 22. M. H. Chisholm, W. W. Reichert, P. Thornton, J . Am. Chem. Soc., 100, 2744 (1978); M. H. Chisholm, F. A. Cotton, M. W. Extine, W. W. Reichert, Inorg. Chem., 17, 2944 (1978); M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 901 (1980). 23. M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine, D. A. Haitko, D. Little, P. E. Fanwick, Inorg. Chem., 18, 2266 (1979). 24. D. C. Bradley, M. H. Chisholm, M. W. Extine, M. E. Stage, lnorg. Chem., 16, 1794 (1977). 25. R. C. Mehrotra, Ado. Inorg. Chem. Radiochem., 26, 280 (1983).
1. 2. .3 4. 5.
3.8.2.4.3 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
Oxidation reactions of transition and inner transition metal-ligand bonds with ROH are rare. Photolytic decarbonylation of Cr(CO),Ar in presence of MeOH forms Cr(OMe)31: 2Cr(C0)3Ar + 6MeOH-
2Cr(OMe)3 + 6CO
+ 2Ar + 3H2
(4
Reactions of Nb(NEtz)4 with i-PrOH and t-BuOH yield Nb(OR)52: 2Nb(NEt2)4
+ lOROH-
2Nb(OR)5 + Et2NH
+ H2
(b)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 69 3.8.2.4 From Alcohols and Phenols 3.8.2.4.3 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
Alkane solutions of W(NMe2)6 react smoothly, but relatively slowly with ROH (R = Me, Et, n-Pr, i-Pr, and CH2=CHCHz)z4yielding alkoxides, W(OR)6: W(NMed4
+ 6ROH-
W(OR)6
+ 6MezNH
However, t-BuOH and t-BuCH,OH fail to react to any appreciable extent at RT. In refluxing C6H6 with r-BuOH, a slow reaction yields W O ( O B U - ~ ) ~ ~ ~ , ~ ~ . (R. C. MEHROTRA, 6.S. SARASWAT) D. C. Bradley, R. C. Mehrotra, D. P. Gaur, Metal Alkoxides,Academic Press, London, 1978. D. L. Kepert, T h e Early Transition Metals, Academic Press, London, 1972, p. 175 D. C. Bradley, R. K. Multani, W. Wardlaw, J . Chem. SOC.,4647 (1958). H. Funk, H. Naumann, 2. Anorg. Allg. Chem., 343 294 (1966). Yu. V. Basikhin, P. P. Rodionov, N. P. Sysoeva, K. P. Lel'kin, Khim. Promst., Ser: Reakt, Osobo Chist. Veshchestu., 11 (1979); Chem. Abstr., 91, 1 8 5 8 3 3 ~(1979). 6. E. W. Ebel, G. Farrow, I. D. H. Towle, J.Chem. Soc., Dalton Trans., 71 (1979). 7. G. Wilke, G. Hermann, Angew. Chem., lnt. Ed. Engl., 5, 581 (1966). 8. S . Komiya, S . Tane-ichi, A. Yamamoto, T. Yamamoto, Bull. Chem. Soc. Jpn., 53, 673 (1980). 9. P. C. Bharara, V. D. Gupta, R. C. Mehrotra, Orgnomet. Chem. Rev., 5, 259 (1977). 10. M. H. Chisholm, F. A. Cotton, M. W. Extine, D. C. Redeout, Inorg. Chem., 18, 120 (1979). 11. M. Brunelli, G. Perego, G. Lugli, A. Mazzei, J . Chem. Soc., Dalton Trans., 861 (1979). 12. M. F. Lappert, P. P. Power, A. R. Sanger, R. C. Srivastava, Metal and Metalloid Amides, Ellis Horwood, Chichester, 1980, p. 610. 13. I. M. Thomas, Can J . Chem., 39, 1386 (1961). 14. M. H. Chisholm, W. Reichert, J . Am. Chem. Soc., 96, 1249 (1974). 15. M. H. Chisholm, M. W. Extine, J . Am. Chem. Soc., 97, 5625 (1975). 16. D.C. Bradley, C. W. Newing, M. H. Chisholm, R. L. Kelly, D. A. Hatko, D. Little, F. A. Cotton, P. E. Fanwick, Inorg. Chem., 19, 3010 (1980). 17. B. Horvath, R. Moseler, E. G. Horvath, Z . Anorg. Allg. Chem., 449, 41 (1979). 18. B. Horvath, E. G. Horvath, 2. Anorg. Allg. Chem., 457, 51 (1979). 19. M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 1863 (1980). 20. M. H. Chisholm. F. A. Cotton, C. A. Murillo, Inorg. Chem., 16, 180 (1977). 21. M. H. Chisholm, W. W. Reichert, F. A. Cotton, C. A. Murillo, J . Am. Chem. Soc.,99,1652 (1977). 22. M. H. Chisholm, W. W. Reichert, P. Thornton, J . Am. Chem. Soc., 100, 2744 (1978); M. H. Chisholm, F. A. Cotton, M. W. Extine, W. W. Reichert, Inorg. Chem., 17, 2944 (1978); M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 901 (1980). 23. M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine, D. A. Haitko, D. Little, P. E. Fanwick, Inorg. Chem., 18, 2266 (1979). 24. D. C. Bradley, M. H. Chisholm, M. W. Extine, M. E. Stage, lnorg. Chem., 16, 1794 (1977). 25. R. C. Mehrotra, Ado. Inorg. Chem. Radiochem., 26, 280 (1983).
1. 2. .3 4. 5.
3.8.2.4.3 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
Oxidation reactions of transition and inner transition metal-ligand bonds with ROH are rare. Photolytic decarbonylation of Cr(CO),Ar in presence of MeOH forms Cr(OMe)31: 2Cr(C0)3Ar + 6MeOH-
2Cr(OMe)3 + 6CO
+ 2Ar + 3H2
(4
Reactions of Nb(NEtz)4 with i-PrOH and t-BuOH yield Nb(OR)52: 2Nb(NEt2)4
+ lOROH-
2Nb(OR)5 + Et2NH
+ H2
(b)
70 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, R2S0, R3P0, R,AsO, etc.) 3.8.2.6.1 By Ligand Substitution with Transition and Inner Transition Complexes
Reaction of [Ti(NMe,),], with PhOH in Et,O at RT similarly yields the adducts3 Ti(OPh)4.Me2NH. Reaction of W2(NMe& with excess i-PrOH in toluene oxidizes W3+ to W4+ and forms W4Hz(OPr-i)144: 2Wz(NMe&
+ 14i-PrOH
-
+
(4
W4H2(OPr-i)14 12Me2NH
However, with excess MeOH and EtOH, tetrameric species [W(OR)4]45 form:
+
2W2(NMe2)6 16ROH-
[W(0R),l4
+ 12Me,NH + 2H2
(4
(R. C. MEHROTRA, B. S. SARASWAT)
1. D. A. Brown, D. Cunningham, W. K. Glass, J . Chem. Soc., Chem. Commun., 306 (1966). 2. I. M. Thomas, Can J . Chern., 39, 1386 (1961); M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 901 (1980). 3. M. F. Lappert, A. R. Sanger, J . Chem. Soc., A , 1314 (1971). 4. M. Akiyama, D. Little, M. H. Chisholm, D. A. Haitko, F. A. Cotton, M. W. Extine, J . Am. Chem. SOC., 101,2504 (1979); M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine, D. A. Haitko, J. Leonelli, D. Little, J . Am. Chem. Soc., 103, 779 (1981). 5. R. C. Mehrotra, Ado. Inorg. Chem. Radiochem., 26, 280 (1983).
3.8.2.5 From Organic Peroxides 3.8.2.5.1 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
, to In a sealed tube reaction at 90”C, CT(C&)~ is oxidized by the ( ~ - B U ) ~inOC6H6 C r ( 0 t - B ~with ) ~ 80% efficiency’. (M. T. POPE) 1. N. Hagihara, H. Yamazaki, J . Am. Chem. Soc., 81, 3160 (1959).
3.8.2.5.2 By Substitution Reactions of Transition and Inner Transition Metal-Ligand Bonds
No reactions of this category appear to have been investigated. (M. T. POPE) 3.8.2.5.3 By Reaction with a Ligand Coordinated to Transition and Inner Transition Metal Elements
No reactions of this category appear to have been investigated. (M. T. POPE)
3.8.2.6 From Neutral Oxygen Donor Ligands (R,CO, R,SO, R,PO, R,AsO, etc.) 3.8.2.6.1 By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes
(i) From (CF,),CO. Reactions of (CF3),C0 with (1,5-C8Hlz)2Ni and (Ph3P),NiC2H4at RT form three-membered ring complexes, ( 1,5-C8H,,) NiOC(CF3)2 u and (Ph3P), NiOC(CF3),, respectively’. Hexafluoroacetone reacts with equimolar d amounts of ML4 (M = Pt, L = Ph3P, MePhzP2; M = Pd, L = Ph3P, MePhzP and
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
70 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, R2S0, R3P0, R,AsO, etc.) 3.8.2.6.1 By Ligand Substitution with Transition and Inner Transition Complexes
Reaction of [Ti(NMe,),], with PhOH in Et,O at RT similarly yields the adducts3 Ti(OPh)4.Me2NH. Reaction of W2(NMe& with excess i-PrOH in toluene oxidizes W3+ to W4+ and forms W4Hz(OPr-i)144: 2Wz(NMe&
+ 14i-PrOH
-
+
(4
W4H2(OPr-i)14 12Me2NH
However, with excess MeOH and EtOH, tetrameric species [W(OR)4]45 form:
+
2W2(NMe2)6 16ROH-
[W(0R),l4
+ 12Me,NH + 2H2
(4
(R. C. MEHROTRA, B. S. SARASWAT)
1. D. A. Brown, D. Cunningham, W. K. Glass, J . Chem. Soc., Chem. Commun., 306 (1966). 2. I. M. Thomas, Can J . Chern., 39, 1386 (1961); M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 901 (1980). 3. M. F. Lappert, A. R. Sanger, J . Chem. Soc., A , 1314 (1971). 4. M. Akiyama, D. Little, M. H. Chisholm, D. A. Haitko, F. A. Cotton, M. W. Extine, J . Am. Chem. SOC., 101,2504 (1979); M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine, D. A. Haitko, J. Leonelli, D. Little, J . Am. Chem. Soc., 103, 779 (1981). 5. R. C. Mehrotra, Ado. Inorg. Chem. Radiochem., 26, 280 (1983).
3.8.2.5 From Organic Peroxides 3.8.2.5.1 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
, to In a sealed tube reaction at 90”C, CT(C&)~ is oxidized by the ( ~ - B U ) ~inOC6H6 C r ( 0 t - B ~with ) ~ 80% efficiency’. (M. T. POPE) 1. N. Hagihara, H. Yamazaki, J . Am. Chem. Soc., 81, 3160 (1959).
3.8.2.5.2 By Substitution Reactions of Transition and Inner Transition Metal-Ligand Bonds
No reactions of this category appear to have been investigated. (M. T. POPE) 3.8.2.5.3 By Reaction with a Ligand Coordinated to Transition and Inner Transition Metal Elements
No reactions of this category appear to have been investigated. (M. T. POPE)
3.8.2.6 From Neutral Oxygen Donor Ligands (R,CO, R,SO, R,PO, R,AsO, etc.) 3.8.2.6.1 By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes
(i) From (CF,),CO. Reactions of (CF3),C0 with (1,5-C8Hlz)2Ni and (Ph3P),NiC2H4at RT form three-membered ring complexes, ( 1,5-C8H,,) NiOC(CF3)2 u and (Ph3P), NiOC(CF3),, respectively’. Hexafluoroacetone reacts with equimolar d amounts of ML4 (M = Pt, L = Ph3P, MePhzP2; M = Pd, L = Ph3P, MePhzP and
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
70 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, R2S0, R3P0, R,AsO, etc.) 3.8.2.6.1 By Ligand Substitution with Transition and Inner Transition Complexes
Reaction of [Ti(NMe,),], with PhOH in Et,O at RT similarly yields the adducts3 Ti(OPh)4.Me2NH. Reaction of W2(NMe& with excess i-PrOH in toluene oxidizes W3+ to W4+ and forms W4Hz(OPr-i)144: 2Wz(NMe&
+ 14i-PrOH
-
+
(4
W4H2(OPr-i)14 12Me2NH
However, with excess MeOH and EtOH, tetrameric species [W(OR)4]45 form:
+
2W2(NMe2)6 16ROH-
[W(0R),l4
+ 12Me,NH + 2H2
(4
(R. C. MEHROTRA, B. S. SARASWAT)
1. D. A. Brown, D. Cunningham, W. K. Glass, J . Chem. Soc., Chem. Commun., 306 (1966). 2. I. M. Thomas, Can J . Chern., 39, 1386 (1961); M. Bochmann, G. Wilkinson, G. B. Young, M. B. Hursthouse, K. M. Abdul Malik, J . Chem. Soc., Dalton Trans., 901 (1980). 3. M. F. Lappert, A. R. Sanger, J . Chem. Soc., A , 1314 (1971). 4. M. Akiyama, D. Little, M. H. Chisholm, D. A. Haitko, F. A. Cotton, M. W. Extine, J . Am. Chem. SOC., 101,2504 (1979); M. Akiyama, M. H. Chisholm, F. A. Cotton, M. W. Extine, D. A. Haitko, J. Leonelli, D. Little, J . Am. Chem. Soc., 103, 779 (1981). 5. R. C. Mehrotra, Ado. Inorg. Chem. Radiochem., 26, 280 (1983).
3.8.2.5 From Organic Peroxides 3.8.2.5.1 By Oxidation of Transition and Inner Transition Metal-Ligand Bonds
, to In a sealed tube reaction at 90”C, CT(C&)~ is oxidized by the ( ~ - B U ) ~inOC6H6 C r ( 0 t - B ~with ) ~ 80% efficiency’. (M. T. POPE) 1. N. Hagihara, H. Yamazaki, J . Am. Chem. Soc., 81, 3160 (1959).
3.8.2.5.2 By Substitution Reactions of Transition and Inner Transition Metal-Ligand Bonds
No reactions of this category appear to have been investigated. (M. T. POPE) 3.8.2.5.3 By Reaction with a Ligand Coordinated to Transition and Inner Transition Metal Elements
No reactions of this category appear to have been investigated. (M. T. POPE)
3.8.2.6 From Neutral Oxygen Donor Ligands (R,CO, R,SO, R,PO, R,AsO, etc.) 3.8.2.6.1 By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes
(i) From (CF,),CO. Reactions of (CF3),C0 with (1,5-C8Hlz)2Ni and (Ph3P),NiC2H4at RT form three-membered ring complexes, ( 1,5-C8H,,) NiOC(CF3)2 u and (Ph3P), NiOC(CF3),, respectively’. Hexafluoroacetone reacts with equimolar d amounts of ML4 (M = Pt, L = Ph3P, MePhzP2; M = Pd, L = Ph3P, MePhzP and
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 71 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, R2S0, R3P0, R3As0, etc.) 3.8.2.6.1 By Ligand Substitution with Transition and Inner Transition Complexes
(PhO),P3) in light petroleum, substituting two ligand moieties to yield similar complexes, e.g.: Pd(PPh3)4
+ (CF,),CO-
(Ph,P),P'C(CF,),
+ 2PPH3
(a)
By contrast, Ni(CNt-Bu),, Pd[P(OMe),I4, Pd[P(OMe),Ph],, and Pd(AsMe,Bz), react with excess (CF3)2C0forming five-membered ring derivatives4, e.g.: Pd[P(OMe),],
+ 2(CF3)2CO-
+
[(Me0)3P]2PdOC(CF3)20C(CF3)2 2P(OMe), (b)
(ii) From R2S0. When excess Me2S0 is added to M(C104), (M = Fe, n = 3; M = Mn, Co, and Ni, n = 2), complexes with composition [M(OSMe,),](C1O4), form'. However, when the halides MX, (M = Co, X = C1 and Br; M = Ni, X = C1) are treated with excess Me,SO, a~tocomplexes~ of the type, [M(OSMe2)6][MX,] result. Similarly, MC14 (M = Th, U, Np, and Pu) react with excess RzSO to yield [ThC13(0SMe2)6]C1637 and [MC1,(OSMe2),] [MC16] (M = U, R = Me8; M = Th, U, and Np, R = Et7;M = U, Np, and Pu, R2 = Ph7; M = Th and U, R = x-C10H7'). (iii) From R3P0 and R3As0. Reaction of M(C104)2 [obtained by dehydration of M(C104)2.6 H 2 0 ) with triethyl orthoformate in EtOH with 4 mol equiv. R 3 E 0 forms [M(OER3),C104](C104) (R3 = Me,, MePh,, and Ph,; E = P, As; M = Mn, Fe, Co, and Ni)'-13. However, similar reaction with excess R 3 E 0 in acetone yields [M(OER,)s](C104)2 (R = Me; E = P and As; M = Co and Ni)10-12,14.Reactions of R 3 P 0 with M(C10& form complexes [M(OPR,)4(C104)z](C104)(R = n-Bu, M = Cr, Fe, and Ce; R = Ph, M = Cr and Ce)9. However, hydroxymethylphosphoramide (HMPA) reacts with M(ClO4)2,M(C104), and M(C104), to yield [M(HMPA),](C104), (M = Mn, Fe, Co, and Ni)9, [M(HMPA),](Clo,), (M = Cr, Fe, Sc, Y, and La-Lu, excluding Pm)9, and [M(HMPA)5](C104)4 (M = U)", respectively. Reactions of Me,PO with MCI, (M = Th, Pa, U, and Np) and Cs,[PuCl,] in MezCO or MeCN solution yield [ M C ~ ( O P M ~ , ) ~ ] C ~ JMe3As0 ' ~ - ' ~ . similarly, reacts with UBr4.4MeCN forming complex [ U ( o A ~ h f e ~ ) ~ ] B r , ' ~ . (R. C. MEHROTRA, 6.S.SARASWAT)
1. E. Uhlig, D. Walther, Coord. Chem. Ren., 33,3 (1980);J. Browning, C. S. Cundy, M. Green, F. G. A. Stone, J . Chem. Soc., A , 20 (1969);A. Ashley-Smith, M. Green, F. G. A. Stone, J . Chem. Soc., A , 3019 (1969). 2. B. Clarke, M. Green, R. B. L. Osborn, F. G. A. Stone, J . Chem. Soc., A , 168 (1968). 3. H. D. Empsall, M. Green, F. G. A. Stone, J . Chem. Soc., Dalton Trans., 96 (1972). 4. M. Green, S. K. Shakshooki, F. G. A. Stone, J . Chem. Soc., A , 2828 (1971). 5. W. L. Reynolds, Prog. Inorg. Chem., 12, 1 (1971). 6. J. L. Ryan, Inorg. Chem., 3, 211 (1964). 7. P. J. Alvey, K. W. Bagnall, D. Brown, J. Edwards, J . Chem. Soc., Dalton Trans., 2308 (1973). 8. J. G. H. du Preez, M. L. Gibson, J . Inorg. Nucl. Chem., 36, 1795 (1974); G. Bombieri, J . Chem. Soc., Chem. Commun., 188 (1975). 9. N. M. Karayannis, C. M. Mikulski, L. L. Pytlewski, Inorg. Chim. Acta, 5 , 69 (1971). 10. A. M. Brodie, S. H. Hunter, G. A. Rodley, C. J. Wilkins, Inorg. Chim. Acta, 2, 195 (1968). 11. S. H. Hunter, R. S. Nyholm, G. A. Rodley, Inorg. Chim. Acta, 3, 631 (1969). 12. S. H. Hunter, E. Emerson, G. A. Rodley, J . Chem. Soc., Chem. Commun., 1398 (1969). 13. J. Lewis, R. S. Nyholnr, G. A. Rodley, Nature, 207, 72 (1965). 14. Y. S . Ng, G. A. Rodley, W. T. Robinson, Inorg. Chem., 15, 303 (1976). 15. J. G. H. du Preez, H. E. Rohwer, Inorg. Nucl. Chem. Lett., 8, 921 (1972).
72 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, &SO, R3P0, RJsO, etc.) 3.8.2.6.3 By Oxidation of the Transition and Inner Transition Metal Complexes 16. Z. M. S . Al-Kazzaz, K. W. Bagnall, D. Brown, J . Inorg. Nucl. Chem., 35, 1493 (1973). 17. G. Bombieri, E. Forsellini, D. Brown, B. Whittaker, J . Chem. SOC.,Dalton Trans., 735 (1976). 18. J. G. H. du Preez, B. J. Gellatly, M. L. Gibson, J . Chem. Soc., Dalton Trans., 1062 (1977). 3.8.2.6.2 By Insertion into Transition and Inner Transition Metal-Ligand Bonds: R'R'CO
-
Acetone reacts with Cp2ZrH2in T H F forming Cp,Zr(OCHMe2)21:
+
Cp2ZrH2 2Me2C0
Cp2Zr(OCHMe2)2
Reaction of (Ph3P),P&0 at RT with excess aldehydes and ketones in C& Pt(I1) ozonide complexes2, e.g.: (Ph3P),P&0 (R'
= H,
+ R'R2CO-
(a) forms
(Ph,P),PtO. OC(R'R2)0
(b)
R2 = Me and Et; R' = Me, R2 = Me and C1CH2)
However, (Ph3P),Pt0. 0 reacts with (CF3),C0 in CH2Clzin both 1: 1 as well as 1: 2 mol ratio to yield five-%seven-membered ring complexes3: (Ph3P)ZPa.P (Ph3P)ZPa.P
+ (CF3)ZCO-
+ 2(CF3)2CO+
(Ph3P)2PtO'OC(CF3)20
(Ph3P)2PtO.O.C(CF3)20C(CF3)20
(4
(d)
When the complexes IrX(CO)L20.0 react even with excess of (CF3)2C0,only 1: 1 insertion products are formed4: IrX(CO)L20.0
(X = C1, Br, I, L
=
+ (CF,),CO-
Ph3P; X
=
X(CO)L21r0.0.C(CF3)20
(4
C1, L = P(Me)Ph2,P(C6H&k-p)3, and Ph3As)
Reaction of (CF3)2C0with (1,5-C8H12)zPtin C6Hs at RT yields a novel 1 : 1 insertion product ':
-
Reactions of P h 2 C 0 with ~ - B U N = T ~ ( N result M ~ ~in) ~the insertion of P h 2 C 0 into the Ta-N bonds, retaining the Ta=N bond? ~ - B u N = T ~ ( N M+ ~ ,2Ph2C0 )~
~ - B U N = T ~ [ O C ( P ~ ~ ) N M ~ ~(g)] ~ ( N M ~ ~ (R. C. MEHROTRA, B. S. SARASWAT)
P. C. Wails, H. Weigold, J . Organomet. Chem., 24, 413 (1970). P. J. Hayward, D. M. Blake, G. Wilkinson, C. J. Nyman, J . Am. Chem. Soc., 92, 5873 (1970). P. J. Hayward, C. J. Nyman, J . Am. Chem. SOC.,93, 617 (1971). W. B. Beaulieu, G. D. Mercer, D. M. Roundhill, J . Am. Chem. Soc., 100, 1147 (1978). M. Green, J. A. K. Howard,A. L. Laguna, L. E. Smart, J. L. Spencer, F. G. A. Stone, J . Chem. SOC., Dalton Trans., 278 (1977). 6. W. A. Nugent, R. L. Harlow, J . Chem. Soc., Chem. Commun., 579 (1978).
1. 2. 3. 4. 5.
3.8.2.6.3 By Oxidation of the Transition and Inner Transition Metal Complexes (Ligand Degradation, Oxygen Abstraction)
Oxygen abstraction reactions are best represented by the halides of Nb(V), Ta(V), Mo(V), and W(V1). Reaction between oxygen-containing ligands and MX5 (M = Nb(V),
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
72 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, &SO, R3P0, RJsO, etc.) 3.8.2.6.3 By Oxidation of the Transition and Inner Transition Metal Complexes 16. Z. M. S . Al-Kazzaz, K. W. Bagnall, D. Brown, J . Inorg. Nucl. Chem., 35, 1493 (1973). 17. G. Bombieri, E. Forsellini, D. Brown, B. Whittaker, J . Chem. SOC.,Dalton Trans., 735 (1976). 18. J. G. H. du Preez, B. J. Gellatly, M. L. Gibson, J . Chem. Soc., Dalton Trans., 1062 (1977). 3.8.2.6.2 By Insertion into Transition and Inner Transition Metal-Ligand Bonds: R'R'CO
-
Acetone reacts with Cp2ZrH2in T H F forming Cp,Zr(OCHMe2)21:
+
Cp2ZrH2 2Me2C0
Cp2Zr(OCHMe2)2
Reaction of (Ph3P),P&0 at RT with excess aldehydes and ketones in C& Pt(I1) ozonide complexes2, e.g.: (Ph3P),P&0 (R'
= H,
+ R'R2CO-
(a) forms
(Ph,P),PtO. OC(R'R2)0
(b)
R2 = Me and Et; R' = Me, R2 = Me and C1CH2)
However, (Ph3P),Pt0. 0 reacts with (CF3),C0 in CH2Clzin both 1: 1 as well as 1: 2 mol ratio to yield five-%seven-membered ring complexes3: (Ph3P)ZPa.P (Ph3P)ZPa.P
+ (CF3)ZCO-
+ 2(CF3)2CO+
(Ph3P)2PtO'OC(CF3)20
(Ph3P)2PtO.O.C(CF3)20C(CF3)20
(4
(d)
When the complexes IrX(CO)L20.0 react even with excess of (CF3)2C0,only 1: 1 insertion products are formed4: IrX(CO)L20.0
(X = C1, Br, I, L
=
+ (CF,),CO-
Ph3P; X
=
X(CO)L21r0.0.C(CF3)20
(4
C1, L = P(Me)Ph2,P(C6H&k-p)3, and Ph3As)
Reaction of (CF3)2C0with (1,5-C8H12)zPtin C6Hs at RT yields a novel 1 : 1 insertion product ':
-
Reactions of P h 2 C 0 with ~ - B U N = T ~ ( N result M ~ ~in) ~the insertion of P h 2 C 0 into the Ta-N bonds, retaining the Ta=N bond? ~ - B u N = T ~ ( N M+ ~ ,2Ph2C0 )~
~ - B U N = T ~ [ O C ( P ~ ~ ) N M ~ ~(g)] ~ ( N M ~ ~ (R. C. MEHROTRA, B. S. SARASWAT)
P. C. Wails, H. Weigold, J . Organomet. Chem., 24, 413 (1970). P. J. Hayward, D. M. Blake, G. Wilkinson, C. J. Nyman, J . Am. Chem. Soc., 92, 5873 (1970). P. J. Hayward, C. J. Nyman, J . Am. Chem. SOC.,93, 617 (1971). W. B. Beaulieu, G. D. Mercer, D. M. Roundhill, J . Am. Chem. Soc., 100, 1147 (1978). M. Green, J. A. K. Howard,A. L. Laguna, L. E. Smart, J. L. Spencer, F. G. A. Stone, J . Chem. SOC., Dalton Trans., 278 (1977). 6. W. A. Nugent, R. L. Harlow, J . Chem. Soc., Chem. Commun., 579 (1978).
1. 2. 3. 4. 5.
3.8.2.6.3 By Oxidation of the Transition and Inner Transition Metal Complexes (Ligand Degradation, Oxygen Abstraction)
Oxygen abstraction reactions are best represented by the halides of Nb(V), Ta(V), Mo(V), and W(V1). Reaction between oxygen-containing ligands and MX5 (M = Nb(V),
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
72 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.6 Neutral Oxygen Donor Ligands (R2C0, &SO, R3P0, RJsO, etc.) 3.8.2.6.3 By Oxidation of the Transition and Inner Transition Metal Complexes 16. Z. M. S . Al-Kazzaz, K. W. Bagnall, D. Brown, J . Inorg. Nucl. Chem., 35, 1493 (1973). 17. G. Bombieri, E. Forsellini, D. Brown, B. Whittaker, J . Chem. SOC.,Dalton Trans., 735 (1976). 18. J. G. H. du Preez, B. J. Gellatly, M. L. Gibson, J . Chem. Soc., Dalton Trans., 1062 (1977). 3.8.2.6.2 By Insertion into Transition and Inner Transition Metal-Ligand Bonds: R'R'CO
-
Acetone reacts with Cp2ZrH2in T H F forming Cp,Zr(OCHMe2)21:
+
Cp2ZrH2 2Me2C0
Cp2Zr(OCHMe2)2
Reaction of (Ph3P),P&0 at RT with excess aldehydes and ketones in C& Pt(I1) ozonide complexes2, e.g.: (Ph3P),P&0 (R'
= H,
+ R'R2CO-
(a) forms
(Ph,P),PtO. OC(R'R2)0
(b)
R2 = Me and Et; R' = Me, R2 = Me and C1CH2)
However, (Ph3P),Pt0. 0 reacts with (CF3),C0 in CH2Clzin both 1: 1 as well as 1: 2 mol ratio to yield five-%seven-membered ring complexes3: (Ph3P)ZPa.P (Ph3P)ZPa.P
+ (CF3)ZCO-
+ 2(CF3)2CO+
(Ph3P)2PtO'OC(CF3)20
(Ph3P)2PtO.O.C(CF3)20C(CF3)20
(4
(d)
When the complexes IrX(CO)L20.0 react even with excess of (CF3)2C0,only 1: 1 insertion products are formed4: IrX(CO)L20.0
(X = C1, Br, I, L
=
+ (CF,),CO-
Ph3P; X
=
X(CO)L21r0.0.C(CF3)20
(4
C1, L = P(Me)Ph2,P(C6H&k-p)3, and Ph3As)
Reaction of (CF3)2C0with (1,5-C8H12)zPtin C6Hs at RT yields a novel 1 : 1 insertion product ':
-
Reactions of P h 2 C 0 with ~ - B U N = T ~ ( N result M ~ ~in) ~the insertion of P h 2 C 0 into the Ta-N bonds, retaining the Ta=N bond? ~ - B u N = T ~ ( N M+ ~ ,2Ph2C0 )~
~ - B U N = T ~ [ O C ( P ~ ~ ) N M ~ ~(g)] ~ ( N M ~ ~ (R. C. MEHROTRA, B. S. SARASWAT)
P. C. Wails, H. Weigold, J . Organomet. Chem., 24, 413 (1970). P. J. Hayward, D. M. Blake, G. Wilkinson, C. J. Nyman, J . Am. Chem. Soc., 92, 5873 (1970). P. J. Hayward, C. J. Nyman, J . Am. Chem. SOC.,93, 617 (1971). W. B. Beaulieu, G. D. Mercer, D. M. Roundhill, J . Am. Chem. Soc., 100, 1147 (1978). M. Green, J. A. K. Howard,A. L. Laguna, L. E. Smart, J. L. Spencer, F. G. A. Stone, J . Chem. SOC., Dalton Trans., 278 (1977). 6. W. A. Nugent, R. L. Harlow, J . Chem. Soc., Chem. Commun., 579 (1978).
1. 2. 3. 4. 5.
3.8.2.6.3 By Oxidation of the Transition and Inner Transition Metal Complexes (Ligand Degradation, Oxygen Abstraction)
Oxygen abstraction reactions are best represented by the halides of Nb(V), Ta(V), Mo(V), and W(V1). Reaction between oxygen-containing ligands and MX5 (M = Nb(V),
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 73 3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands 3.8.2.7.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
Ta(V),X = C1 and Br) under mild conditions forms adducts of MX51. With excess ligand or under more vigorous conditions, however, oxygen abstraction occurs from ethers2, ~ u l f o x i d e s ~phosphine ,~, and arsine oxides4., (e.g., NbC1, forms NbOCl,. 2Me2S0 together with C1CH2SCH3 and HCI with excess M e 2 S 0 at RT3): NbC1,
+ 3Me2SO-
NbOC13.2Me2S0
+ ClCH2SCH3+ HCl
(a)
Similarly, with excess P h 3 P 0 5 , Ph3As06, and TMU7, NbOC13.2L compounds form. However, NbC15 and TaCI, abstract oxygen from (Me2N),P0 forming complexes MOCl,. 2(Me2N),P08 only after refluxing a mixture of reactants in CCI4 for 6 h. Molybdenum(V) chloride reacts with oxygen-containing ligands with abstraction of oxygen to form green oxomolybdenum complexes'. In 1,4-dioxane, MoC1,. C4H802 is formed initially, but after some weeks in solvent at RT the complexes MoOCl, (C&02)1,5 and C1(CH2)20(CH2)2C1are obtained. Similarly, in THF, MoOCI, '2THF and CI(CH2),CI formg. Reaction of MoCl, with P h 3 P 0 in CH2C12-CC14 yields a mixture of MoOCl,. 2 P h 3 P 0 and MoOzC12.2Ph3P0. However, in EtOH solution only the former is formed". Reaction of MoCl, with excess Me2SO" and Ph2SO11,similarly, gives the MoOCl, . 2R2S0 (R = Me and Ph) complexes. Few oxygen abstraction reactions of WCl, are known'. However, WC16 reacts in M e 2 C 0 or D M F with Me2S0, (CH2),S0, and (Me2N),P0 to yield the complexes w02c12. 2L12. (R. C. MEHROTRA, B. S. SARASWAT) 1. D. L. Kepert, The Early Transition Metals, Academic Press, London, 1972. 2. D. B. Copley, F. Fairbrother, A. Thompson, J . Chem. Soc., 315 (1964);A. Cowley, F. Fairbrother, N. Scott, J . Chem. Soc., 3133 (1958); K. Feenan, G. W. A. Fowles, J . Chem. Soc., 2499 (1965). 3. D. B. Copley, F. Fairbrother, K. H. Grundy, A. Thompson, J . Less-Common Met., 6,407 (1964). 4. C. Santini-Scampucci, J. G. Riess, J . Chem. Soc., Dalton Trans., 1433 (1974). 5. D. B. Copley, F. Fairbrother, A. Thompson, J . Less-Common Met., 8, 256 (1965). 6. D. Brown, J. F. Easey, J. G. H. du Preez, J . Chem. Soc., A , 258 (1966). 7. A. 0. Baghlaf, K. Behzadi, A. Thompson, J . Less-Common Met., 61, 31 (1978). 8. J. R. Dorschner, J . Inorg. Nucl. Chem., 34, 2665 (1972); K. Behzadi, A. Thompson, J . LessCommon Met., 56, 9 (1977). 9. D. L. Kepert, R. Madyczewsky, J . Chem. Soc., A , 530 (1968). 10. S. M. Horner, S . Y. Tyree, Jr., Inorg. Chem., 1, 122 (1962). 11. K. Behzadi, A. 0. Baghlaf, A. Thompson, J . Less-Common Met., 57, 103 (1978). 12. B. J. Brisdon, Inorg. Chem., 6, 1791 (1967).
3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands (Crown Ethers, Macrocycles, P,CPentanedione, etc.) 3.8.2.7.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
(i) From Crown Ethers. Reaction of CoCI2 with syn-di(cis-cyclohexyl)-l8-crown-6 (sdc-6) in AcOH forms the complex', [Co(sdc-6)][CoC14]:
2CoCIZ
+ S~C-6-
[ C O ( S ~ C -[ ~C)O] C ~ ~ ]
(a)
Halides MXz [M = Co(I1) and Ni(II), X = C1 and Br] similarly react with 18-crown-6in a mixture of Et20-MeOH yielding the ionic complexes', [M(18-crown-6)] [MX,]. The polyether benzo-15-crown-5 reacts with Ln(NO,),. 6 H 2 0 in MezCO yielding [Ln(NO,), (benzo-l5-crown-5)] complexes with lighter lanthanides (Ln = La, Ce, Pr,
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 73 3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands 3.8.2.7.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
Ta(V),X = C1 and Br) under mild conditions forms adducts of MX51. With excess ligand or under more vigorous conditions, however, oxygen abstraction occurs from ethers2, ~ u l f o x i d e s ~phosphine ,~, and arsine oxides4., (e.g., NbC1, forms NbOCl,. 2Me2S0 together with C1CH2SCH3 and HCI with excess M e 2 S 0 at RT3): NbC1,
+ 3Me2SO-
NbOC13.2Me2S0
+ ClCH2SCH3+ HCl
(a)
Similarly, with excess P h 3 P 0 5 , Ph3As06, and TMU7, NbOC13.2L compounds form. However, NbC15 and TaCI, abstract oxygen from (Me2N),P0 forming complexes MOCl,. 2(Me2N),P08 only after refluxing a mixture of reactants in CCI4 for 6 h. Molybdenum(V) chloride reacts with oxygen-containing ligands with abstraction of oxygen to form green oxomolybdenum complexes'. In 1,4-dioxane, MoC1,. C4H802 is formed initially, but after some weeks in solvent at RT the complexes MoOCl, (C&02)1,5 and C1(CH2)20(CH2)2C1are obtained. Similarly, in THF, MoOCI, '2THF and CI(CH2),CI formg. Reaction of MoCl, with P h 3 P 0 in CH2C12-CC14 yields a mixture of MoOCl,. 2 P h 3 P 0 and MoOzC12.2Ph3P0. However, in EtOH solution only the former is formed". Reaction of MoCl, with excess Me2SO" and Ph2SO11,similarly, gives the MoOCl, . 2R2S0 (R = Me and Ph) complexes. Few oxygen abstraction reactions of WCl, are known'. However, WC16 reacts in M e 2 C 0 or D M F with Me2S0, (CH2),S0, and (Me2N),P0 to yield the complexes w02c12. 2L12. (R. C. MEHROTRA, B. S. SARASWAT) 1. D. L. Kepert, The Early Transition Metals, Academic Press, London, 1972. 2. D. B. Copley, F. Fairbrother, A. Thompson, J . Chem. Soc., 315 (1964);A. Cowley, F. Fairbrother, N. Scott, J . Chem. Soc., 3133 (1958); K. Feenan, G. W. A. Fowles, J . Chem. Soc., 2499 (1965). 3. D. B. Copley, F. Fairbrother, K. H. Grundy, A. Thompson, J . Less-Common Met., 6,407 (1964). 4. C. Santini-Scampucci, J. G. Riess, J . Chem. Soc., Dalton Trans., 1433 (1974). 5. D. B. Copley, F. Fairbrother, A. Thompson, J . Less-Common Met., 8, 256 (1965). 6. D. Brown, J. F. Easey, J. G. H. du Preez, J . Chem. Soc., A , 258 (1966). 7. A. 0. Baghlaf, K. Behzadi, A. Thompson, J . Less-Common Met., 61, 31 (1978). 8. J. R. Dorschner, J . Inorg. Nucl. Chem., 34, 2665 (1972); K. Behzadi, A. Thompson, J . LessCommon Met., 56, 9 (1977). 9. D. L. Kepert, R. Madyczewsky, J . Chem. Soc., A , 530 (1968). 10. S. M. Horner, S . Y. Tyree, Jr., Inorg. Chem., 1, 122 (1962). 11. K. Behzadi, A. 0. Baghlaf, A. Thompson, J . Less-Common Met., 57, 103 (1978). 12. B. J. Brisdon, Inorg. Chem., 6, 1791 (1967).
3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands (Crown Ethers, Macrocycles, P,CPentanedione, etc.) 3.8.2.7.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
(i) From Crown Ethers. Reaction of CoCI2 with syn-di(cis-cyclohexyl)-l8-crown-6 (sdc-6) in AcOH forms the complex', [Co(sdc-6)][CoC14]:
2CoCIZ
+ S~C-6-
[ C O ( S ~ C -[ ~C)O] C ~ ~ ]
(a)
Halides MXz [M = Co(I1) and Ni(II), X = C1 and Br] similarly react with 18-crown-6in a mixture of Et20-MeOH yielding the ionic complexes', [M(18-crown-6)] [MX,]. The polyether benzo-15-crown-5 reacts with Ln(NO,),. 6 H 2 0 in MezCO yielding [Ln(NO,), (benzo-l5-crown-5)] complexes with lighter lanthanides (Ln = La, Ce, Pr,
74
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands 3.8.2.7.1 Substitution of Transition and Inner Transition Metal-Ligand Bonds
Nd, and Sm) and of the type [Ln(N03)3(benzo-15-crown-5)]~ 3 H 2 0 . M e 2 C 0 with heavier lanthanons (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu). However, the ligand dibenzo-18-crown-6 under similar conditions forms [Ln(N03)3(dibenzo-18crown-6)] complexes with La, Ce, Pr, and Nd only3. When reacted with Ln(N03)3.6 H 2 0 in EtzO-EtOH, syn-di(cis-cyclohexy1)-18crown-6 yields, a crystalline complex [La(N03),(sdc-6)], which was the first uncharged 12-coordinated complex to be studied by X-ray crystallography4. Among the actinides, UC14 reacts with sdc-6 forming a complex [UC13(sdc-6)],[UC1,], and the reaction of UC13(THF), (prepared in situ) with 18-crown-6 in T H F solution yields [UC13(18-crown6)15. The crown ethers, 15-crown-5 and 18-crown-6, yield [Ln(N03)3(15-crown-5)] (Ln = La-Gd) and [Ln(N03)3(18-crown-6)] (Ln = La-Nd) complexes, respectively6. Reactions of anhydrous L I I ( C ~ O with ~ ) ~ 12-crown-4, 15-crown-5, and dibenzo-30crown-10 in MeCN form the ionic complexes [Ln(l2-~rown-4),](ClO~)~ (Ln = La, Pr, Eu, Ho, Er, Tm and Yb)?, [Pr(l2-crown-4)(15-cro~n-5)](ClO~)~, CPr(l5-crown5)J (C104)38,and [Ln(dibenzo-30-crown-10)](C104)3 (Ln = La, Ce, Pr, Nd, Sm, and E u ) ~respectively. , However, the macrocycle dibenzo-18-crown-6 reacts with Ln(C104), yielding neutral complexes of type, [LII(C~O,)~(dibenzo-18-crown-6)]~ x H 2 0 (Ln = La, Ce, Pr, Nd, Sm, Eu, Dy, and Ho, x = 0; Ln = Er and Yb, x = 1)”. (ii) From Cryptands. Reaction of cryptand-221 with Co(SCN), in CHC13 yields complex [Co(cryptand-221)] [CO(SCN)~]having its seven-coordinated Co(I1) atom completely enclosed in the polyether ligand”. The cryptand-222 reacts with La(N03)3 forming the complexes [La(cryptand-222)(N03),], [La(N03)6]’2 and [Sm(cryptand222)(N03)], [Sm(N03)5Hz0]’3, respectively. However, it reacts with Ln(C104)3 in MeCN yielding 1: 1 complexes of type, [Ln(cryptand-222)C104] (C104)2.MeCN, where Ln = La, Ce, Pr, N d , Sm, a n d E u ’ ~ . (iii) From p-Diketones (p-dk). Reactions of /I-dkH with MCl, in non aqueous solvents form partially substituted derivatives like M(acac),Cl, (M = Til5,I6,V’?, Mo’*, and W”), Zr(acac),C116, and P a ( a ~ a c ) ~ C l ~ l ~ . Although Z r ( a ~ a c )10H202’, ~, Zr(hfac),, and H f ( h f a ~ ) ~can ” be prepared by the reactions of MC14 with H(acac) and H(hfac) in H 2 0with refluxing CC14,respectively, the P-diketonate complexes of Zr(IV)19, Hf(IV)”, Th(IV)19, U(IV)”, Ln(III)23,Fe(III)24, Cr(III)”, and CO(II)’~are best synthesized by metathesis of MC1, with P-dkH in the presence of bases like NH3, C5H5N,C5HloNH,NHzCONHz, CH3COONa, or NaOH in aqueous or non aqueous media, e.g.:
MC14 + 4H(acac) + 4C5Hl0NH-
M(acac),
+ 4C5HloNH.HCl
(b)
(M = Zr, Hf, and Th) FeC13
+ 3H(tfac) + 3CH3COONa-%+
+
F e ( t f a ~ ) ~3NaC1
+ 3CH3COOH
(c)
(R. C.MEHROTRA, 6.S. SARASWAT) 1. A. C. L. Su, J. F. Weiher, Inorg. Chem., 7, 176 (1968). 2. D. de Vos, J. van Daalen, A. C . Knegt, T. C. van Heyningen, L. P. Otto, M. W. Vonk, A. J. M. Wijsman, W. L. Driessen, J . Inorg. Nucl. Chem., 37, 1319 (1975). 3. R. B. King, P. R. Heckley, J . Am. Chem. SOC.,96, 3 118 (1974). 4. M. E. Harman, F. A. Hart, M. B. Hursthouse, G. P. Moss, P. R. Raithby, J . Chem. SOC.,Chem. Commun., 396 (1976).
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 75 3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands 3.8.2.7.2 By Oxidation of Transition and Inner Transition Metal Complexes 5. G. C. de Villardi, P. Charpin, R. M. Costes, G. Folcher, P. Plurien, P. Ringy, C. de Rango, J . Chem. SOC.,Chem. Commun., 90 (1978); D. C. Moody, R. E. Penneman, K. V. Salazar, Inorg. Chem., 18, 208 (1979). 6. J. C. G. Bunzli, D. Wessner, Helv. Chim. Acta, 61, 1454 (1978). 7. J. F. Desreux, G. Duyckaerts, Inorg. Chim. Acta, 35, L313 (1979). 8. J. C. G. Bunzli, D. Wessner, H. T. T. Oanh, Inorg. Chim. Acta, 32, L33 (1979). 9. M. Ciampolini, N. Nardi, Inorg. Chim. Acta, 32, L9 (1979). 10. M. Ciampolini, N. Nardi, R. Cini, S. Mangani, P. Orioli, J . Chem. SOC., Dalton Trans., 1983 (1979). 11. F. Mathieu, R. Weiss, J . Chem. Soc., Chem. Commun., 816 (1973). 12. F. A. Hart, M. B. Hursthouse, K. M. A. Abdul Malik, S. Moorhouse, J . Chem. Soc., Chem. Commun., 549, (1978). 13. J. H. Burns, Inorg. Chem., 18, 3044 (1979). 14. M. Ciampolini, P. Dapporto, N. Nardi, J . Chem. SOC.,Chem. Commun.,788 (1978); J . Chem. SOC., Dalton Trans., 974 (1979). 15. K. C. Pande, R. C. Mehrotra, Chem. Ind. (London), 35, 1198 (1958). 16. R. C. Mehrotra, R. Bohra, D. P. Gaur, Metal P-Diketonates and Allied Deriaatiaes, Academic Press, London, 1978; R. C. Mehrotra, Pure Appl. Chem., 60, 1349 (1988). 17. R. B. Von Dreele, R. C. Fray, J . Am. Chem. SOC., 94, 7935 (1972). 18. G. Doyle, Inorg. Chem., 10, 2348 (1971). 19. D. Brown, B. Whittaker, J. Tacon, J . Chem. SOC., Dalton Trans., 34 (1975). 20. G. T. Morgan, A. R. Bowen, J . Chem. SOC.,125, 1259 (1924). 21. M. L. Morris, R. W. Moshier, R. E. Sievers, Inorg. Synth., 9,50 (1967); S. Chattoraj, C. T. Lynch, K. S. Mazdiyasni, Inorg. Chem., 7, 2501 (1968). 22. H. I. Schlesinger, H. C. Brown, J. J .Katz, S. Archer, R. A. Laid, J . Am. Chem. SOC., 78, 2790 (1956). 23. R. G. Charles, A. Perrotto, J . Inorg. Nucl. Chem., 16, 373 (1964); R. A. Lalancette, M. Cefola, W. C. Hamilton, S. J. L. Placa, Inorg. Chem., 6, 2127 (1967); R. C. Mehrotra, J. M. Batwara, Coord. Chem. ReG., 31, 67 (1980). 24. R. N. Haszeldine, W. K. R. Musgrave, F. Smith, L. M. Turtan, J . Chem. SOC., 609 (1951). 25. K. C. Joshi, V. N. Pathak, J . Chem. SOC., Perkin Trans. 1, 57 (1973). 26. A. Syamal, J . Indian Chem. Soc., 45, 719 (1968). 3.8.2.7.2 By Oxidation of Transition and Inner Transition Metal Complexes
In reactions of metal carbonyls with P-diketones, the metals are oxidized t o the higher oxidation states by formation of metal P-diketonatesl, e.g.,on heating a mixture of a metal carbonyl with an excess of P-diketones under reflux in an inert atmosphere of Nz gas, metal /I-diketones form: 2M(CO),
+ 6P-dkH-
2M(P-dk),
+ 3H2 + 2nC0
(a) (M = Fe, n = 5, P-dk = acacZs3;M = Cr and Mo, n = 6, P-dk = acac and hfac3.,) Metal P-diketonates also form upon irradiating a mixture of metal carbonyls and P-diketones with ultraviolet light in a refluxing solvent like n-C6HI4,C6H6, CCl,, or (i-c3 H 7) 2 0 : 2M(CO), (M
= Cr,
n
=
+ 6P-dkH-
6, P-dk
= acac
2M(P-dk), and hfac; M
+ 3H2 + 2nC0
= Mo,
P-dk = acac, n
(b) =
6)
In the reaction of C O ~ ( C Owith ) ~ hfac under refluxing conditions, Co(hfac), 2 H z 0 forms as a major product, with Co(hfac), in trace quantities6. Reaction of Mo(C,H,)(dppe), with H(acac) in refluxing toluene results in the formation of an acetylacetonate derivative’: Mo(C,H,)(dppe),
+ H(acac)-
+
MoH(acac)(dppe)z CzH4
(4
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 75 3.8.2.7 From Bidentate and Polydentate Oxygen Donor Ligands 3.8.2.7.2 By Oxidation of Transition and Inner Transition Metal Complexes 5. G. C. de Villardi, P. Charpin, R. M. Costes, G. Folcher, P. Plurien, P. Ringy, C. de Rango, J . Chem. SOC.,Chem. Commun., 90 (1978); D. C. Moody, R. E. Penneman, K. V. Salazar, Inorg. Chem., 18, 208 (1979). 6. J. C. G. Bunzli, D. Wessner, Helv. Chim. Acta, 61, 1454 (1978). 7. J. F. Desreux, G. Duyckaerts, Inorg. Chim. Acta, 35, L313 (1979). 8. J. C. G. Bunzli, D. Wessner, H. T. T. Oanh, Inorg. Chim. Acta, 32, L33 (1979). 9. M. Ciampolini, N. Nardi, Inorg. Chim. Acta, 32, L9 (1979). 10. M. Ciampolini, N. Nardi, R. Cini, S. Mangani, P. Orioli, J . Chem. SOC., Dalton Trans., 1983 (1979). 11. F. Mathieu, R. Weiss, J . Chem. Soc., Chem. Commun., 816 (1973). 12. F. A. Hart, M. B. Hursthouse, K. M. A. Abdul Malik, S. Moorhouse, J . Chem. Soc., Chem. Commun., 549, (1978). 13. J. H. Burns, Inorg. Chem., 18, 3044 (1979). 14. M. Ciampolini, P. Dapporto, N. Nardi, J . Chem. SOC.,Chem. Commun.,788 (1978); J . Chem. SOC., Dalton Trans., 974 (1979). 15. K. C. Pande, R. C. Mehrotra, Chem. Ind. (London), 35, 1198 (1958). 16. R. C. Mehrotra, R. Bohra, D. P. Gaur, Metal P-Diketonates and Allied Deriaatiaes, Academic Press, London, 1978; R. C. Mehrotra, Pure Appl. Chem., 60, 1349 (1988). 17. R. B. Von Dreele, R. C. Fray, J . Am. Chem. SOC., 94, 7935 (1972). 18. G. Doyle, Inorg. Chem., 10, 2348 (1971). 19. D. Brown, B. Whittaker, J. Tacon, J . Chem. SOC., Dalton Trans., 34 (1975). 20. G. T. Morgan, A. R. Bowen, J . Chem. SOC.,125, 1259 (1924). 21. M. L. Morris, R. W. Moshier, R. E. Sievers, Inorg. Synth., 9,50 (1967); S. Chattoraj, C. T. Lynch, K. S. Mazdiyasni, Inorg. Chem., 7, 2501 (1968). 22. H. I. Schlesinger, H. C. Brown, J. J .Katz, S. Archer, R. A. Laid, J . Am. Chem. SOC., 78, 2790 (1956). 23. R. G. Charles, A. Perrotto, J . Inorg. Nucl. Chem., 16, 373 (1964); R. A. Lalancette, M. Cefola, W. C. Hamilton, S. J. L. Placa, Inorg. Chem., 6, 2127 (1967); R. C. Mehrotra, J. M. Batwara, Coord. Chem. ReG., 31, 67 (1980). 24. R. N. Haszeldine, W. K. R. Musgrave, F. Smith, L. M. Turtan, J . Chem. SOC., 609 (1951). 25. K. C. Joshi, V. N. Pathak, J . Chem. SOC., Perkin Trans. 1, 57 (1973). 26. A. Syamal, J . Indian Chem. Soc., 45, 719 (1968). 3.8.2.7.2 By Oxidation of Transition and Inner Transition Metal Complexes
In reactions of metal carbonyls with P-diketones, the metals are oxidized t o the higher oxidation states by formation of metal P-diketonatesl, e.g.,on heating a mixture of a metal carbonyl with an excess of P-diketones under reflux in an inert atmosphere of Nz gas, metal /I-diketones form: 2M(CO),
(M = Fe, n
=
5, P-dk
+ 6P-dkH-
2M(P-dk),
= acacZs3; M = Cr
+ 3H2 + 2nC0
and Mo, n
=
6, P-dk
= acac
(a) and hfac3.,)
Metal P-diketonates also form upon irradiating a mixture of metal carbonyls and P-diketones with ultraviolet light in a refluxing solvent like n-C6HI4,C6H6, CCl,, or (i-c3 H 7) 2 0 : 2M(CO), (M
= Cr,
n
=
+ 6P-dkH-
6, P-dk
= acac
2M(P-dk), and hfac; M
+ 3H2 + 2nC0
= Mo,
P-dk = acac, n
(b) =
6)
In the reaction of C O ~ ( C Owith ) ~ hfac under refluxing conditions, Co(hfac), 2 H z 0 forms as a major product, with Co(hfac), in trace quantities6. Reaction of Mo(C,H,)(dppe), with H(acac) in refluxing toluene results in the formation of an acetylacetonate derivative’: Mo(C,H,)(dppe),
+ H(acac)-
+
MoH(acac)(dppe)z CzH4
(4
76
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.8. From Main Group Element Oxides 3.8.2.8.2 By Insertion into Transition and Inner Transition Metal Bonds
Refluxing equimolar mixtures of R U ( C O ) , ( P P ~ ~and )~ MeOCHzCHzOH yields R u ( a c a ~ ) H ( C 0 ) ( P P h ~ ) ~ ~ : Ru(C0),(PPh3),
+ H(acac)-
Ru(acac)H(CO)(PPh,),
H(acac) in
+ 2CO
2-
(4
(R. C. MEHROTRA, B. S. SARASWAT) 1. R. C. Mehrotra, R. Bohra, D. P. Gaur, Metal, 8-Diketonates, and Allied Derivatil;es, Academic Press, London, 1978; R. C. Mehrotra, Pure Appl. Chem., 60, 1349 (1988). 2. H. Reihlen, A. Gruhl, G. V. Hessling, Justus Liebigs Ann. Chem., 472, 268 (1929). 3. M. Dunne, F. A. Cotton, Inorg. Chem., 2, 263 (1963). 4. M. L. Larson, F. W. Moore, Inorg. Chem., I , 856 (1962). 5. J. C. Goan, C. H. Huether, H. E. Podall, Inorg. Chem., 2, 1078 (1963). 6. M. Kilner, F. A. Hartman, A. Wojcicki, Inorg. Chem., 6, 406 (1967). 7. T. Ito, T. Kokubo, T. Yamamoto, A. Yamamoto, S. Ikeda, J . Chem. Soc., Dalton Trans., 1783 (1974). 8. M. A. M. Queiros, S . D. Robinson, Inorg. Chem., 17, 310 (1978).
3.8.2.8.From Main Group Element Oxides 3.8.2.8.1 By Direct Addition to the Transition and Inner Transition Metals and Their Complexes
Reactions involving COz, NOz, NzO4, and SOzare in this category. Weak dihapto (C, 0)complexes are formed by addition of COz to Ni(PL3)3(L = cyclohexyl, Et, n-Bu) in toluene. Treatment 0 f [ 1 r C l ( C ~ H ~ ~ ) ( P M ewith , ) ~ l COz in benzene gives the C,Obonded chelate [IrC1(OCOCOz)(PMe3),]. Formation of [L3(CO)FeC03]from reaction of COz with L4Fe (L = phosphine) in pentane at 0°C involves an intermediate with dihapto COz'. Most SO, complexes of the transition metals are S-bonded but [Rh(NO)SO,(PPh,),], formed from [RhNO(PPh,),], contains dihapto SOz. Liquid SO2 reacts with several metal halides producing oxohalides and SOXz e.g., NbOC1, from NbC15, WOCl4 from WC16; WOZBrzfrom wB1-6; UOZCl2from UClS2. Such reactions are usually carried out in a bomb at 60-70°C. Solid state reactions yield MOClZ (M = Ti, Zr, Pa, Th, U, and Np) from the tetrahalides and A s 2 0 3 or SbzO3 at 200-400°C. Titanium and Zr tetrahalides react with N z 0 4 in CC14 forming MO(N03)2.The tetranitrates form in neat NzO4.
(M.T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Adl;. Catal., 28, 79 (1979). 2. W. Karcher, H. Hecht, in Chemistry in Nonaqueous Ionizing Solvents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, eds., Pergamon Press, New York, 1967, p. 79. 3.8.2.8.2 By Insertion into Transition and Inner Transition Metal Bonds
Carbon dioxide inserts into metal-H, -C, and -N bonds'. In most cases, insertion into an M-H bond leads to a formate complex, e.g.: [(Ph,P)3Co(Nz)H]
+ COz
--+
[(Ph,P),Co(OOCH)]
+ Nz
Two molecules of COz can be inserted, as in formation of [L3Fe(00CH)J from [(EtPh2P),FeH4] in sunlight. No reaction occurs in the dark or in light at 0°C. Reaction of [L4RuHz] with C 0 2 occurs slowly in toluene yielding [L,RuH(OOCH)] only when L = PPh3. With L = PPh2H, PPhzMe, and PPhMez, no reaction is observed. Insertion of C 0 2 into Ti-, Zr-, Co-, Ni-, and Rh-C bonds leads to carboxylato
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
76
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.8. From Main Group Element Oxides 3.8.2.8.2 By Insertion into Transition and Inner Transition Metal Bonds
Refluxing equimolar mixtures of R U ( C O ) , ( P P ~ ~and )~ MeOCHzCHzOH yields R u ( a c a ~ ) H ( C 0 ) ( P P h ~ ) ~ ~ : Ru(C0),(PPh3),
+ H(acac)-
Ru(acac)H(CO)(PPh,),
H(acac) in
+ 2CO
2-
(4
(R. C. MEHROTRA, B. S. SARASWAT) 1. R. C. Mehrotra, R. Bohra, D. P. Gaur, Metal, 8-Diketonates, and Allied Derivatil;es, Academic Press, London, 1978; R. C. Mehrotra, Pure Appl. Chem., 60, 1349 (1988). 2. H. Reihlen, A. Gruhl, G. V. Hessling, Justus Liebigs Ann. Chem., 472, 268 (1929). 3. M. Dunne, F. A. Cotton, Inorg. Chem., 2, 263 (1963). 4. M. L. Larson, F. W. Moore, Inorg. Chem., I , 856 (1962). 5. J. C. Goan, C. H. Huether, H. E. Podall, Inorg. Chem., 2, 1078 (1963). 6. M. Kilner, F. A. Hartman, A. Wojcicki, Inorg. Chem., 6, 406 (1967). 7. T. Ito, T. Kokubo, T. Yamamoto, A. Yamamoto, S. Ikeda, J . Chem. Soc., Dalton Trans., 1783 (1974). 8. M. A. M. Queiros, S . D. Robinson, Inorg. Chem., 17, 310 (1978).
3.8.2.8.From Main Group Element Oxides 3.8.2.8.1 By Direct Addition to the Transition and Inner Transition Metals and Their Complexes
Reactions involving COz, NOz, NzO4, and SOzare in this category. Weak dihapto (C, 0)complexes are formed by addition of COz to Ni(PL3)3(L = cyclohexyl, Et, n-Bu) in toluene. Treatment 0 f [ 1 r C l ( C ~ H ~ ~ ) ( P M ewith , ) ~ l COz in benzene gives the C,Obonded chelate [IrC1(OCOCOz)(PMe3),]. Formation of [L3(CO)FeC03]from reaction of COz with L4Fe (L = phosphine) in pentane at 0°C involves an intermediate with dihapto COz'. Most SO, complexes of the transition metals are S-bonded but [Rh(NO)SO,(PPh,),], formed from [RhNO(PPh,),], contains dihapto SOz. Liquid SO2 reacts with several metal halides producing oxohalides and SOXz e.g., NbOC1, from NbC15, WOCl4 from WC16; WOZBrzfrom wB1-6; UOZCl2from UClS2. Such reactions are usually carried out in a bomb at 60-70°C. Solid state reactions yield MOClZ (M = Ti, Zr, Pa, Th, U, and Np) from the tetrahalides and A s 2 0 3 or SbzO3 at 200-400°C. Titanium and Zr tetrahalides react with N z 0 4 in CC14 forming MO(N03)2.The tetranitrates form in neat NzO4.
(M.T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Adl;. Catal., 28, 79 (1979). 2. W. Karcher, H. Hecht, in Chemistry in Nonaqueous Ionizing Solvents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, eds., Pergamon Press, New York, 1967, p. 79. 3.8.2.8.2 By Insertion into Transition and Inner Transition Metal Bonds
Carbon dioxide inserts into metal-H, -C, and -N bonds'. In most cases, insertion into an M-H bond leads to a formate complex, e.g.: [(Ph,P)3Co(Nz)H]
+ COz
--+
[(Ph,P),Co(OOCH)]
+ Nz
Two molecules of COz can be inserted, as in formation of [L3Fe(00CH)J from [(EtPh2P),FeH4] in sunlight. No reaction occurs in the dark or in light at 0°C. Reaction of [L4RuHz] with C 0 2 occurs slowly in toluene yielding [L,RuH(OOCH)] only when L = PPh3. With L = PPh2H, PPhzMe, and PPhMez, no reaction is observed. Insertion of C 0 2 into Ti-, Zr-, Co-, Ni-, and Rh-C bonds leads to carboxylato
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
76
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.8. From Main Group Element Oxides 3.8.2.8.2 By Insertion into Transition and Inner Transition Metal Bonds
Refluxing equimolar mixtures of R U ( C O ) , ( P P ~ ~and )~ MeOCHzCHzOH yields R u ( a c a ~ ) H ( C 0 ) ( P P h ~ ) ~ ~ : Ru(C0),(PPh3),
+ H(acac)-
Ru(acac)H(CO)(PPh,),
H(acac) in
+ 2CO
2-
(4
(R. C. MEHROTRA, B. S. SARASWAT) 1. R. C. Mehrotra, R. Bohra, D. P. Gaur, Metal, 8-Diketonates, and Allied Derivatil;es, Academic Press, London, 1978; R. C. Mehrotra, Pure Appl. Chem., 60, 1349 (1988). 2. H. Reihlen, A. Gruhl, G. V. Hessling, Justus Liebigs Ann. Chem., 472, 268 (1929). 3. M. Dunne, F. A. Cotton, Inorg. Chem., 2, 263 (1963). 4. M. L. Larson, F. W. Moore, Inorg. Chem., I , 856 (1962). 5. J. C. Goan, C. H. Huether, H. E. Podall, Inorg. Chem., 2, 1078 (1963). 6. M. Kilner, F. A. Hartman, A. Wojcicki, Inorg. Chem., 6, 406 (1967). 7. T. Ito, T. Kokubo, T. Yamamoto, A. Yamamoto, S. Ikeda, J . Chem. Soc., Dalton Trans., 1783 (1974). 8. M. A. M. Queiros, S . D. Robinson, Inorg. Chem., 17, 310 (1978).
3.8.2.8.From Main Group Element Oxides 3.8.2.8.1 By Direct Addition to the Transition and Inner Transition Metals and Their Complexes
Reactions involving COz, NOz, NzO4, and SOzare in this category. Weak dihapto (C, 0)complexes are formed by addition of COz to Ni(PL3)3(L = cyclohexyl, Et, n-Bu) in toluene. Treatment 0 f [ 1 r C l ( C ~ H ~ ~ ) ( P M ewith , ) ~ l COz in benzene gives the C,Obonded chelate [IrC1(OCOCOz)(PMe3),]. Formation of [L3(CO)FeC03]from reaction of COz with L4Fe (L = phosphine) in pentane at 0°C involves an intermediate with dihapto COz'. Most SO, complexes of the transition metals are S-bonded but [Rh(NO)SO,(PPh,),], formed from [RhNO(PPh,),], contains dihapto SOz. Liquid SO2 reacts with several metal halides producing oxohalides and SOXz e.g., NbOC1, from NbC15, WOCl4 from WC16; WOZBrzfrom wB1-6; UOZCl2from UClS2. Such reactions are usually carried out in a bomb at 60-70°C. Solid state reactions yield MOClZ (M = Ti, Zr, Pa, Th, U, and Np) from the tetrahalides and A s 2 0 3 or SbzO3 at 200-400°C. Titanium and Zr tetrahalides react with N z 0 4 in CC14 forming MO(N03)2.The tetranitrates form in neat NzO4.
(M.T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Adl;. Catal., 28, 79 (1979). 2. W. Karcher, H. Hecht, in Chemistry in Nonaqueous Ionizing Solvents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, eds., Pergamon Press, New York, 1967, p. 79. 3.8.2.8.2 By Insertion into Transition and Inner Transition Metal Bonds
Carbon dioxide inserts into metal-H, -C, and -N bonds'. In most cases, insertion into an M-H bond leads to a formate complex, e.g.: [(Ph,P)3Co(Nz)H]
+ COz
--+
[(Ph,P),Co(OOCH)]
+ Nz
Two molecules of COz can be inserted, as in formation of [L3Fe(00CH)J from [(EtPh2P),FeH4] in sunlight. No reaction occurs in the dark or in light at 0°C. Reaction of [L4RuHz] with C 0 2 occurs slowly in toluene yielding [L,RuH(OOCH)] only when L = PPh3. With L = PPh2H, PPhzMe, and PPhMez, no reaction is observed. Insertion of C 0 2 into Ti-, Zr-, Co-, Ni-, and Rh-C bonds leads to carboxylato
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.8. From Main Group Element Oxides 3.8.2.8.3 By Oxidation of Transition and Inner Transition Metals
77
complexes. Reaction is exemplified by formation of [(PhCHzCOO),(PhCHz),Ti] from [(PhCH,),Ti] under mild conditions. The corresponding reaction of the Zr complex is two orders of magnitude faster. With [Cp,TiPh,], the product of C 0 2 insertion at 80°C is the C,O-bonded chelate [Cp,TiC6H4C00]. Insertion into the Rh-C bond occurs with [Rh(Ph)(PPh,),] and C 0 2 at 20 atm and RT, and with [Ni(C,H,),(bipy)] in benzene at 40-50°C and atmospheric pressure. The latter reaction leads to both monoand dipropionato complexes and to [Ni(bipy)(C03)]. Insertion into benzylchromium complexes does not occur, although reaction occurs between [Cr(CHZC6H4-o-NMe2),] and one C 0 2 . Carbon dioxide insertion into metal-nitrogen bonds occurs readily with dialkylamido complexes Cr[N(i-PrZ)l3, M ( N R z ) ~(M = Ti, Zr, V, Th, U), M’(NMe& (M’ = Nb, Ta), W(NMe2)6,and W2(NMe2)6.Th products are the corresponding N , N dialkylcarbamato complexes, M(02CNR2),, and in the case of the W compounds, W(NMe2)3(02CNMe2)3 and Wz(02CNMe2)6respectively’32. Sulfur dioxide insertion reactions leading to metal-oxygen bonds are rare. An example is the BF3/SbF5-promotedreaction of [CpW(CO),R] (R = Me, Bz) with liquid SO2 to give [CpW(CO),OS(OBF,)R]. In the absence of promoters, the product is an S-sulfinato complex3. (M. T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Adu. Catal., 28, 79 (1979). 2. F. Calderazzo, G. Dell’amico, R. Netti, M. Pasquali, Inorg. Chem., 17, 471 (1978). 3. R. G. Severson, A. Wojcicki, J . Am. Chem. Soc., 101, 817 (1979). 3.8.2.8.3 By Oxidation of Transition and Inner Transition Metals and Their Compounds
Metal reactions with N2O4 and SO2 are promoted by solvents such as MeCOOEt and M e N 0 2 . Thus, V, Mn, Co, and U dissolve in N204/MeCOOEt yielding the anhydrous nitrates or oxonitrates [V02N03,UOz(N03)2];however, Cr, Fe, Ni, and Pt are unreactive’. Metal disulfates are formed when Ti, V, Mn, Fe, Co, and Ni dissolve in S02/Me2S0.These metals are insoluble in either solvent separately. Products of dissolution of Ce, Pr, Eu, Dy, and U in S02/Me2S0 have not been characterized2. Liquid N 2 0 4 reacts vigorously with Ni(C0)4 and Fe(CO),, but less rapidly with C O ~ ( C OMn2(CO)lo, )~, Cr(C0)6,M o ( C O ) ~and , W(CO)6,to give anhydrous nitrates or nitrato complexes. Dinitrogen pentoxide reacts analogously. Gaseous NOz reacts with [Pt(PPh3)2C2H4]yielding [Pt(PPh3),(NO)(N03)] and oxidizes [Ir(PPh3),(CO)Cl] to
CI~(PP~~)~(CO)C~(NO~)(N~Z)I ’.
Reaction of COz with some early transition metal complexes in toluene leads to deoxygenation or disproportionation and reduction4: [Cp,TiCl12 4[Cp,Ti(CO),]
+ C02
[Cp2TiC1],0
+ CO
(a)
+ 4 C 0 2 A [ ( C P ~ T ~ ) ~ ( C+O lOC0 ~)]~
(b)
+ 3coz I [Cp2Zr013+ 9CO
(4
3[Cp2Zr(C0)2]
52 C Zdarr
1 4 C 4dayi
(M. T. POPE)
1. C. C. Addison, in Chemistry in Nonaqueous Ionizing Solvents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, eds., Pergamon Press, New York, 1967, p. 1.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.8. From Main Group Element Oxides 3.8.2.8.3 By Oxidation of Transition and Inner Transition Metals
77
complexes. Reaction is exemplified by formation of [(PhCHzCOO),(PhCHz),Ti] from [(PhCH,),Ti] under mild conditions. The corresponding reaction of the Zr complex is two orders of magnitude faster. With [Cp,TiPh,], the product of C 0 2 insertion at 80°C is the C,O-bonded chelate [Cp,TiC6H4C00]. Insertion into the Rh-C bond occurs with [Rh(Ph)(PPh,),] and C 0 2 at 20 atm and RT, and with [Ni(C,H,),(bipy)] in benzene at 40-50°C and atmospheric pressure. The latter reaction leads to both monoand dipropionato complexes and to [Ni(bipy)(C03)]. Insertion into benzylchromium complexes does not occur, although reaction occurs between [Cr(CHZC6H4-o-NMe2),] and one C 0 2 . Carbon dioxide insertion into metal-nitrogen bonds occurs readily with dialkylamido complexes Cr[N(i-PrZ)l3, M ( N R z ) ~(M = Ti, Zr, V, Th, U), M’(NMe& (M’ = Nb, Ta), W(NMe2)6,and W2(NMe2)6.Th products are the corresponding N , N dialkylcarbamato complexes, M(02CNR2),, and in the case of the W compounds, W(NMe2)3(02CNMe2)3 and Wz(02CNMe2)6respectively’32. Sulfur dioxide insertion reactions leading to metal-oxygen bonds are rare. An example is the BF3/SbF5-promotedreaction of [CpW(CO),R] (R = Me, Bz) with liquid SO2 to give [CpW(CO),OS(OBF,)R]. In the absence of promoters, the product is an S-sulfinato complex3. (M. T. POPE)
1. R. Eisenberg, D. E. Hendriksen, Adu. Catal., 28, 79 (1979). 2. F. Calderazzo, G. Dell’amico, R. Netti, M. Pasquali, Inorg. Chem., 17, 471 (1978). 3. R. G. Severson, A. Wojcicki, J . Am. Chem. Soc., 101, 817 (1979). 3.8.2.8.3 By Oxidation of Transition and Inner Transition Metals and Their Compounds
Metal reactions with N2O4 and SO2 are promoted by solvents such as MeCOOEt and M e N 0 2 . Thus, V, Mn, Co, and U dissolve in N204/MeCOOEt yielding the anhydrous nitrates or oxonitrates [V02N03,UOz(N03)2];however, Cr, Fe, Ni, and Pt are unreactive’. Metal disulfates are formed when Ti, V, Mn, Fe, Co, and Ni dissolve in S02/Me2S0.These metals are insoluble in either solvent separately. Products of dissolution of Ce, Pr, Eu, Dy, and U in S02/Me2S0 have not been characterized2. Liquid N 2 0 4 reacts vigorously with Ni(C0)4 and Fe(CO),, but less rapidly with C O ~ ( C OMn2(CO)lo, )~, Cr(C0)6,M o ( C O ) ~and , W(CO)6,to give anhydrous nitrates or nitrato complexes. Dinitrogen pentoxide reacts analogously. Gaseous NOz reacts with [Pt(PPh3)2C2H4]yielding [Pt(PPh3),(NO)(N03)] and oxidizes [Ir(PPh3),(CO)Cl] to
CI~(PP~~)~(CO)C~(NO~)(N~Z)I ’.
Reaction of COz with some early transition metal complexes in toluene leads to deoxygenation or disproportionation and reduction4: [Cp,TiCl12 4[Cp,Ti(CO),]
+ C02
[Cp2TiC1],0
+ CO
(a)
+ 4 C 0 2 A [ ( C P ~ T ~ ) ~ ( C+O lOC0 ~)]~
(b)
+ 3coz I [Cp2Zr013+ 9CO
(4
3[Cp2Zr(C0)2]
52 C Zdarr
1 4 C 4dayi
(M. T. POPE)
1. C. C. Addison, in Chemistry in Nonaqueous Ionizing Solvents, Vol. 111, G. Jander, H. Spandau, C. C. Addison, eds., Pergamon Press, New York, 1967, p. 1.
78
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond O,; and 053.8.2.9 From OH-,02-, 3.8.2.9.1 By Ligand Substitution with Transition and Inner Transition Metal
2. W. D. Harrison, J. B. Gill, D. C. Goodall, J . Chem. SOC.,Dalton Trans., 847 (1979). 3. M. Kubota, C. A. Koerntgen, G. W. McDonald, Inorg. Chim. Acta, 30, 119 (1978). 4. G. Fachinetti, C. Floriani, A. Chiesi-Villa, C. Guastini, J . Am. Chem. SOC.,101; 1767 (1979).
3.8.2.9 From OH-, 02-,O;, and 0;3.8.2.9.1 By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes
Precipitation of metal hydroxides by addition of O H - t o solutions of metal complexes is governed by the relative magnitudes of the solubility products of the hydroxides (Table 1) and by the instability constants of the complexes1. For substitution-inert octahedral complexes of Cr3+, Co3+, Rh3+, Ir3', Ru2'I3+, and Pt4', intermediate hydroxo-substituted complexes are isolable:
-
[CO(NH~)~C~]'+ [CO(NH~)~OH]~+
(a)
tr~ns-[Ru(NH~)~(N0)Cl]~' [Ru(NH~)~(NO)OH]'+
(b)
Thus, net reaction involves hydroxide displacement of halide. The mechanism might, however, involve formation of the conjugate base of the amine ~ o m p l e x ' , ~Under . more vigorous conditions, complete substitution occurs: [PtCl,]'-
30
KOH
[Pt(OH),]'-
The ultimate products of the reaction of O H - with high-valent halides of group VA, VIA, and VIIA metals are the oxyanions of these metals. Reactions may proceed as direct TABLE1.
SOLUBILITY PRODUCTS OF
Metal v3+
voz+ Cr3+ Mn2Fe2' Fe3' co2+ co3+ Ni2' Zr4Hf4* PdZ+
log K,, - 34.4
- 23.5 - 29.8 - 12.8 - 15.1 - 38.8 - 14.9 - 44.5 (19°C) - 15.2 - 54.1 - 54.8 - 28.5
TRANSITION METALHYDROXIDES AT 25°C Metal sc3 Y3+ La3+ Ce3+ Pr3+ Nd3' Sm3+ Eu3+ Gd3+ Tb3' Dy3' +
HO~+
Er3+ Yb3+ LU3+
Th4+
u4+
PU4+ "Source: Ref. 1
log K,,
- 32.7 - 23.2 - 20.7 - 21.2 - 21.5 - 23.1 - 25.4 - 25.6 - 25.7 - 25.5 - 25.6 - 25.9 - 24.9 - 25.0 - 26.1 - 49.7 - 56.2 - 47.3
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
78
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond O,; and 053.8.2.9 From OH-,02-, 3.8.2.9.1 By Ligand Substitution with Transition and Inner Transition Metal
2. W. D. Harrison, J. B. Gill, D. C. Goodall, J . Chem. SOC.,Dalton Trans., 847 (1979). 3. M. Kubota, C. A. Koerntgen, G. W. McDonald, Inorg. Chim. Acta, 30, 119 (1978). 4. G. Fachinetti, C. Floriani, A. Chiesi-Villa, C. Guastini, J . Am. Chem. SOC.,101; 1767 (1979).
3.8.2.9 From OH-, 02-,O;, and 0;3.8.2.9.1 By Ligand Substitution Reactions with Transition and Inner Transition Metal Complexes
Precipitation of metal hydroxides by addition of O H - t o solutions of metal complexes is governed by the relative magnitudes of the solubility products of the hydroxides (Table 1) and by the instability constants of the complexes1. For substitution-inert octahedral complexes of Cr3+, Co3+, Rh3+, Ir3', Ru2'I3+, and Pt4', intermediate hydroxo-substituted complexes are isolable:
-
[CO(NH~)~C~]'+ [CO(NH~)~OH]~+
(a)
tr~ns-[Ru(NH~)~(N0)Cl]~' [Ru(NH~)~(NO)OH]'+
(b)
Thus, net reaction involves hydroxide displacement of halide. The mechanism might, however, involve formation of the conjugate base of the amine ~ o m p l e x ' , ~Under . more vigorous conditions, complete substitution occurs: [PtCl,]'-
30
KOH
[Pt(OH),]'-
The ultimate products of the reaction of O H - with high-valent halides of group VA, VIA, and VIIA metals are the oxyanions of these metals. Reactions may proceed as direct TABLE1.
SOLUBILITY PRODUCTS OF
Metal v3+
voz+ Cr3+ Mn2Fe2' Fe3' co2+ co3+ Ni2' Zr4Hf4* PdZ+
log K,, - 34.4
- 23.5 - 29.8 - 12.8 - 15.1 - 38.8 - 14.9 - 44.5 (19°C) - 15.2 - 54.1 - 54.8 - 28.5
TRANSITION METALHYDROXIDES AT 25°C Metal sc3 Y3+ La3+ Ce3+ Pr3+ Nd3' Sm3+ Eu3+ Gd3+ Tb3' Dy3' +
HO~+
Er3+ Yb3+ LU3+
Th4+
u4+
PU4+ "Source: Ref. 1
log K,,
- 32.7 - 23.2 - 20.7 - 21.2 - 21.5 - 23.1 - 25.4 - 25.6 - 25.7 - 25.5 - 25.6 - 25.9 - 24.9 - 25.0 - 26.1 - 49.7 - 56.2 - 47.3
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 79 3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.1 0.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds hydroly ses: NbC15
[Nb6019]'-
or they may involve disproportionation:
3ReC1,
2Re02 + R e 0 4
(g)
Superoxides of La, Pr, Nd, and Dy are obtained by reaction of NaOz with the perchlorates dissolved in liquid NH34. (M. T. POPE) 1. R. M. Smith, A. E. Martell, eds., Critical Stability Constants, Vol. 4, Plenum Press, New York, 1976. 2. F. Basolo, R. G. Pearson, Mechanisms of Inorganic Reactions, 2nd ed., Wiley, New York, 1967. 3. J. P. Candlin, K. A. Taylor, D. Y. Thompson, Reactions of Transition Metal Complexes, Elsevier, New York, 1968. 4. V. N. Belevskii, E. Romashov, A. E. Kharakoz, T. B. Durnyakova, S. V. Bleshinksii, I n . Akad. Nauk Kirg. SSR, 57 (1975); Chem. Abstr., 83, 88117r (1975). 3.8.2.9.2 By Oxidation of the Transition and Inner Transition Metals and Their Complexes
In the absence of air, Mn dissolves in 20-50% NaOH yielding H z and Na,[Mn(OH),]. Other metals that react with aqueous NaOH are Nb, Mo, W, Os, and Eu. The products are, respectively, [Nb6Ol9]'-, MOO:-, WOj-, [OSO,(OH),]~-, and Eu(OH), .HzO. Iron is anodically oxidized in K O H solution to give KZFeO4. Reaction of metals with fused NaOH, Na,O, or Na2OZappears not to have been exhaustively investigated; few results have been reported for either series of the inner transition elements, although U reacts in alkaline H 2 0 2 or aqueous N a z 0 2 forming uncharacterized peroxouranates. Among the transition elements Cr is oxidized by NaOH (800°C, N z atmosphere) to C r 2 0 3 , and by NazOz to Na2Cr04; Co, Mn, Ni, Os, and Rh are converted to COO, MnO,, NiO, Os04, and R h 2 0 3 , and Ti, V, Nb, Ta, Mo, and W are converted to oxoanion salts by fused NaOH. The remaining platinum metals (Ru, Ir, Pd, Pt) are attacked by NazO, at red heat forming oxides (e.g.,4 N a 2 0 Ir03).Metallic Zr and Hf are virtually inert toward fused NaZO2'. (M. T. POPE) 1. J. P. Candlin, K. A. Taylor, D. Y. Thompson, Reactions of Transition Metal Complexes, Elsevier, New York, 1968.
3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.10.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
(i) [RO] - . Starting with the synthesis of VO(0Et)i and Ti(OEt):, soluble primary and secondary alkoxides of transition and inner transition metals [Th(IV), U(IV), W(V),
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 79 3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.1 0.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds hydroly ses: NbC15
[Nb6019]'-
or they may involve disproportionation:
3ReC1,
2Re02 + R e 0 4
(g)
Superoxides of La, Pr, Nd, and Dy are obtained by reaction of NaOz with the perchlorates dissolved in liquid NH34. (M. T. POPE) 1. R. M. Smith, A. E. Martell, eds., Critical Stability Constants, Vol. 4, Plenum Press, New York, 1976. 2. F. Basolo, R. G. Pearson, Mechanisms of Inorganic Reactions, 2nd ed., Wiley, New York, 1967. 3. J. P. Candlin, K. A. Taylor, D. Y. Thompson, Reactions of Transition Metal Complexes, Elsevier, New York, 1968. 4. V. N. Belevskii, E. Romashov, A. E. Kharakoz, T. B. Durnyakova, S. V. Bleshinksii, I n . Akad. Nauk Kirg. SSR, 57 (1975); Chem. Abstr., 83, 88117r (1975). 3.8.2.9.2 By Oxidation of the Transition and Inner Transition Metals and Their Complexes
In the absence of air, Mn dissolves in 20-50% NaOH yielding H z and Na,[Mn(OH),]. Other metals that react with aqueous NaOH are Nb, Mo, W, Os, and Eu. The products are, respectively, [Nb6Ol9]'-, MOO:-, WOj-, [OSO,(OH),]~-, and Eu(OH), .HzO. Iron is anodically oxidized in K O H solution to give KZFeO4. Reaction of metals with fused NaOH, Na,O, or Na2OZappears not to have been exhaustively investigated; few results have been reported for either series of the inner transition elements, although U reacts in alkaline H 2 0 2 or aqueous N a z 0 2 forming uncharacterized peroxouranates. Among the transition elements Cr is oxidized by NaOH (800°C, N z atmosphere) to C r 2 0 3 , and by NazOz to Na2Cr04; Co, Mn, Ni, Os, and Rh are converted to COO, MnO,, NiO, Os04, and R h 2 0 3 , and Ti, V, Nb, Ta, Mo, and W are converted to oxoanion salts by fused NaOH. The remaining platinum metals (Ru, Ir, Pd, Pt) are attacked by NazO, at red heat forming oxides (e.g.,4 N a 2 0 Ir03).Metallic Zr and Hf are virtually inert toward fused NaZO2'. (M. T. POPE) 1. J. P. Candlin, K. A. Taylor, D. Y. Thompson, Reactions of Transition Metal Complexes, Elsevier, New York, 1968.
3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.10.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
(i) [RO] - . Starting with the synthesis of VO(0Et)i and Ti(OEt):, soluble primary and secondary alkoxides of transition and inner transition metals [Th(IV), U(IV), W(V),
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 79 3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.1 0.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds hydroly ses: NbC15
[Nb6019]'-
or they may involve disproportionation:
3ReC1,
2Re02 + R e 0 4
(g)
Superoxides of La, Pr, Nd, and Dy are obtained by reaction of NaOz with the perchlorates dissolved in liquid NH34. (M. T. POPE) 1. R. M. Smith, A. E. Martell, eds., Critical Stability Constants, Vol. 4, Plenum Press, New York, 1976. 2. F. Basolo, R. G. Pearson, Mechanisms of Inorganic Reactions, 2nd ed., Wiley, New York, 1967. 3. J. P. Candlin, K. A. Taylor, D. Y. Thompson, Reactions of Transition Metal Complexes, Elsevier, New York, 1968. 4. V. N. Belevskii, E. Romashov, A. E. Kharakoz, T. B. Durnyakova, S. V. Bleshinksii, I n . Akad. Nauk Kirg. SSR, 57 (1975); Chem. Abstr., 83, 88117r (1975). 3.8.2.9.2 By Oxidation of the Transition and Inner Transition Metals and Their Complexes
In the absence of air, Mn dissolves in 20-50% NaOH yielding H z and Na,[Mn(OH),]. Other metals that react with aqueous NaOH are Nb, Mo, W, Os, and Eu. The products are, respectively, [Nb6Ol9]'-, MOO:-, WOj-, [OSO,(OH),]~-, and Eu(OH), .HzO. Iron is anodically oxidized in K O H solution to give KZFeO4. Reaction of metals with fused NaOH, Na,O, or Na2OZappears not to have been exhaustively investigated; few results have been reported for either series of the inner transition elements, although U reacts in alkaline H 2 0 2 or aqueous N a z 0 2 forming uncharacterized peroxouranates. Among the transition elements Cr is oxidized by NaOH (800°C, N z atmosphere) to C r 2 0 3 , and by NazOz to Na2Cr04; Co, Mn, Ni, Os, and Rh are converted to COO, MnO,, NiO, Os04, and R h 2 0 3 , and Ti, V, Nb, Ta, Mo, and W are converted to oxoanion salts by fused NaOH. The remaining platinum metals (Ru, Ir, Pd, Pt) are attacked by NazO, at red heat forming oxides (e.g.,4 N a 2 0 Ir03).Metallic Zr and Hf are virtually inert toward fused NaZO2'. (M. T. POPE) 1. J. P. Candlin, K. A. Taylor, D. Y. Thompson, Reactions of Transition Metal Complexes, Elsevier, New York, 1968.
3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.10.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
(i) [RO] - . Starting with the synthesis of VO(0Et)i and Ti(OEt):, soluble primary and secondary alkoxides of transition and inner transition metals [Th(IV), U(IV), W(V),
80 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 0 From Alkoxide and Carboxylate Anions 3.8.2.10.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
La(III), Pr(III), Nd(III), Sm(III), Y(III), Yb(III), Er(III), Gd(III), Ho(III), Pa(V), Ni(II), and Cr(III)] are prepared by reactions of MCl, with NaOR in excess ROH and a hydrocarbon solvent such as benzene3-': MCl,
+ nNaOR-M(OR),
+ nNaCl
(a) For preparation of methoxides (insoluble in organic solvents) of most metals [e.g., Ti(III)6, V(VII)7, Fe(III)6, Cr(III)6,Mn(III)6, Ni(III)6, CO(III)~, Er(III)', Gd(III)', and U(IV)9], reaction of MCl, with LiOMe in MeOH is preferred in view of the ease of separation from the soluble LiC1: MCl,
+ nLiOMe-
M(OMe),
+ n-LiC1
(b) The alkali alkoxide method is sometimes complicated by formation of bimetallic alkoxides with excess MOR33", e.g.:
+ 9NaOi-PrMC15 + 6LiOMe-
2ZrC1,
N a [ Z ~ ~ ( 0 i - P r+) ~8NaCl ]
(4
Li[M(OMe),]
(dl
+ 5LiCI
(M = Nb and Ta) Reaction between LnC13(Ln = Gd, Ho and Er), AlC13, and KOi-Pr in i-PrOH in 1:3:12 mol ratio similarly results in formation of bimetallic isopropoxides' '. LnC13 + 3A1C13 + 12KOi-Pr-
Ln[Al(Oi-Pr),],
+ 12KC1
(el
The lithium alkoxide method can further be extended to synthesize a large number of Co(I1) and Ni(I1) alkoxides that are insoluble in the parent alcohols'2: MC1, [M
= Co(II), R = Me,
+ 2 L i O R z M(OR),l + 2LiCl
Et, and i-Pr; M
= Ni(II), R =
(f)
Me, Et, n-Pr, i-Pr, and t-Bu]
Primary alkoxides of Cr(II1) are prepared by metathesis between CrC13.3THF (which is soluble in organic solvents) and LiOR": CrC13.3THF + 3LiOR
ROH
C6H6
Cr(OR)3 + 3LiCl
(g)
(R = Me, Et, and n-Bu) The C r ( 0 t - B ~cannot )~ be synthesized under the conditions above, but by the reaction of CrC13.3THF with 3 mol equiv. of LiOt-Bu (in the absence of excess of t-BuOH) in THF'~: CrC13.3THF + 3LiOt-Bu-
C r ( 0 t - B ~+ ) ~3LiCl
(h)
In light petroleum at RT, LiOCH(t-Bu), and a small excess of CrC13.3THF give a blue-green solution from which royal blue, air-sensitive crystals of Cr [OCH(~-BU)~] 3. THF are isolated. However, with a slight excess of LiOCH(t-Bu), over CrC13.3THF, dichroic crystals of L ~ C ~ [ O C H ( ~ - B U ) ~ ] are ~ . T~Hb F tained'~. Reaction of ReOC1, in E t 2 0 with a light petroleum solution of LiOt-Bu in a 1 :4 molar ratio at RT yields R e o ( 0 t - B ~ )Metathesis ~. between ReOC1, and LiOi-Pr in 1 : 5 molar ratio in an ether-light petroleum mixture at RT yields a bimetallic isopr~poxide'~: ReOCl,
+ 5LiOi-Pr-
Li[ReO(LOi-Pr)S] .LiCl + 3LiCl
6)
81 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.10 From Alkoxide and Carboxylate Anions 3.8.2.1 0.1 By Substitution of Transition and Inner Transition Metal-Ligand Bonds
Reactions of UC14 and UOz(N03)2.2THFwith NaOC(CF3)3in Et,O-THF solution yield U[OC(CF3)3]4.2THF and UOz [OC(CF3)3]2.2THF,respecti~ely’~. (ii) [RC02]-. Reaction of transition and inner transition metal salts with ammonium or alkali carboxylates in aqueous or alcoholic solution forms transition and inner transition metal carboxylates:
MX,
+ nRC02M’-
M(02CR),
+ nM‘X
(j)
The carboxylates of Cr(III)I6,Fe(II)”, Rh(II)I8,La(III)”, Ce(III)”, Pr(III)”, and Nd” are synthesized by metathesis of soluble metal salts with ammonium or alkali carboxylates, e.g.: MC13
+ 3NaOzCR-
[M = La(II1) and Ce(III), R
=
M(O,CR),
+ 3NaCl
(k)
n-CllH23, n-ClSH31, and n-C17H35]
Anhydrous metallic and organometallic carboxylates form by double decomposition of soluble metallic (organometallic) halides and soluble carboxylates of univalent metals in a suitable organic solvent in which at least one of the products remains insoluble. Thus anhydrous Cr(III), Mn(II), Fe(III), CO(II), and Ni(I1)” trifluoroacetates are prepared by reaction of MC1, with CF3CO2Agin MeN02: MCl,
-
+ n-Ag02CCF3
+
M(02CCF3), n-AgC1
(1)
On refluxing g5-CpZTiClzwith silver or alkali metal acylates in CHC13 or C6H6 under anaerobic conditions, qs-CpzTi(02CR)2are f ~ r m e d ’ .~The , ~ fluorocarboxylates ~ of gs-CpzTi(IV)and q5-Cp,Zr(IV) moieties are also prepared in this manner in benzene or acetonezsJ6:
+
g5-CpzMClZ 2AgOzCR( M = Ti, R
q5-Cp2M(O2CR)z
= CF3; M = Zr,
+ 2AgCl
(m)
R = CF3 and C3F7)
Reactions of Mn(CO)5Br and Re(CO)5Br with CF3CO2Ag in CHzClz yield the corresponding carboxylate derivatives’ 5 , 2 6 . (R. C. MEHROTRA, B. S. SARASWAT)
1. 2. 3. 4. 5.
6. 7. 8. 9. 10. 11. 12. 13. 14.
N. Prandtl, L. Hess, Z . Anorg. Allg. Chem., 82, 103 (1913). F. Bischoff, H. Adkins, J . Am. Chem. Soc., 46, 256 (1924). D. C. Bradley, Prog. Inorg. Chem., 2, 303 (1960). R. C. Mehrotra, Inorg. Chim. Acta, I , 99 (1967). D. C. Bradley, R. C. Mehrotra, D. P. Gaur, Metal Alkoxides, Academic Press, London, 1978. R. W. Adams, E. Bishop, R. L. Martin, G. Winter, Aust. J . Chem., 19, 207 (1966). D. C. Bradley, M. L. Mehta, Can. J . Chem., 40, 1710 (1962). R. C. Mehrotra, J. M. Batwara, Inorg. Chem., 9, 2505 (1970). D. C. Bradley, B. N. Chakravarti, A. K. Chatterjee, J . Inorg. Nucl. Chem., 12, 71 (1959). R. Gut, H e h . Chim. Acta, 47, 2262 (1964); C. J. Ludman, T. C. Waddington, J . Chem. Soc., A , 1816 (1966). R. C. Mehrotra, M. M. Agrawal, A. Mehrotra, Synth. React. Inorg. Met.-Org. Chem., 3, 181 (1973). R. C. Mehrotra, in Coordination Chemistry-21 (IUPAC), J. P. Laurent, ed., Pergamon Press, Oxford, 1981, p. 113. M. Bochmann, G. Wilkinson, G. B. Young, J . Chem. Soc., Dalton, Trans., 1863 (1980). P. G. Edwards, G. Wilkinson, M. B. Hursthouse, K. M. Abdul Malik, J. Chem. SOC.,Dalton Trans., 2467 (1980).
82
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 1 From Metal Atom and Related Reactions 3.8.2.1 1.1 Abstraction and Electron Transfer Processes
15. R. A. Andersen, Inorg. Nucl. Chem. Lett., 15, 57 (1979); R. A. Anderson, Inorg. Chem., 18, 209 (1979). 16. J. H. Balthis, J. G. Bailar, Inorg. Synth., I , 123 (1939); M. R. Hatfield, Inorg. Synth., 3 , 148 (1950). 17. T. Golgotiv, I. Rosca, V. Petracovschi, Bull. Inst. Politch. lasi, 18, 21 (1972); Chem. Abstr., 79, 86925w (1973). 18. L. A. Nazarova, I. I. Chernyaev, A. S. Morozova, Zh. Neorg. Khim., 11, 2583 (1966). 19. S. N. Misra, T. N. Misra, R. C. Mehrotra, J . Inorg. Nucl. Chem., 25, 195 (1963). 20. T. N. Misra, Ph.D. thesis, Rajasthan University, Jaipur, 1963. 21. S. N. Misra, Ph.D. thesis, Rajasthan University, Jaipur, 1964. 22. M. J. Baillie, D. H. Brown, K. C. Moss, D. W. A. Sharp, J . Chem. Soc., A , 3110 (1968). 23. G. A. Razuvaev, V. N. Latyaeva, L. I. Vyshinskaya, Dokl. Akad. Nauk SSSR, 138, 1126 (1961); Chem. Abstr., 55, 27248b (1961). 24. A. N. Nesmeyanov, 0. V. Nogina, A. M. Berlin, A. S. Girshovich, G. V. Shatalov, I z c . Akad. Nauk SSSR, Otd. Khirn. Nauk, 2146 (1961); Chem. Abstr., 57, 11221f (1962). 25. R. B. King, R. N. Kapoor, J . Organomet. Chem., 15,457 (1968). 26. R. B. King, R. N. Kapoor, J . Inorg. Nucl. Chem., 31, 2169 (1969).
3.8.2.11 From Metal Atom and Related Reactions 3.8.2.11.1 Abstraction and Electron Transfer Processes
Transition metal atoms abstract oxygen from epoxides, including cyclohexene oxide1x2.Reaction efficiency, as measured by the amount of cyclohexene produced per metal atom, is Ti = 0.9, V = 2.8, Cr = 2.7, Co = 1.2, and Ni = 0.6: 0
0
+
M
4
0 +
[MO]
Chromium atoms abstract oxygen from 2,6-dimethylpyridine oxide, P h 3 P 0 , Me2S0, and nitro- and nitro~oarenes'-~.For nitro- and nitrosoarenes, nitrene or nitrenoid species are likely intermediates. Atoms of Ti, V, Cr, Co, and Ni also deoxygenate T H F and some ketones in low yield','. In addition, cyclohexanone can be reduced and coupled to 1,l'-bicyclohexyl 1,l'-diol by atoms of the early transition metals; the later transition metals are less reactive6. Iron atoms with ethylene oxide react with spontaneous C-0 insertion to form a matrix-isolated metallaoxetane7~*, Gas phase metal atom reactions, using high temperature, fast-flow reactors (HTFER), have been used in oxygen abstraction processes. The Fe 02-Fe0 0 mL/molg,". reaction at 1330°C proceeds with a rate coefficient of 3.6 x
+
+
(K. J. KLABUNDE)
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
J. Gladysz, J. Fulcher, S. Togashi, J . Org. Chem., 41, 3647 (1976). S. Togashi, J. G. Fulcher, B. R. Cho, M. Hasegawa, J. A. Gladysz, J . Org. Chem., 45,3044 (1980). J. Gladysz, J. Fulcher, S . Togashi, Tetrahedron Lett., 521 (1977). T. Chivers, P. L. Timms, J . Organomet. Chem., 118, C37 (1976). T. 0. Murdock, Ph.D. thesis, University of North Dakota, 1977. J. T. Miller, C. W. Dekock, J . Org. Chem., 46, 516 (1981). 2. Kafafi, R. H. Hauge, W. E. Billups, J. L. Margrave, J . Am. Chem. Soc., 109, 4775 (1987). 2. Kafafi, R. H. Hauge, 3. L. Margrave, J . Am. Chem. Soc., 107, 7550 (1985). A. Fontijn, S. C. Kurzius, J. J. Houghton, J. A. Emerson, Rea. Sci. Instrum., 43, 726 (1972). A. Fontijn, S. C. Kurzius, J. J. Houghton, Proc. Int. Symp. Combust., 14,167(1973); Chem. Abstr., 78, 62775a (1973).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
82
3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 1 From Metal Atom and Related Reactions 3.8.2.1 1.1 Abstraction and Electron Transfer Processes
15. R. A. Andersen, Inorg. Nucl. Chem. Lett., 15, 57 (1979); R. A. Anderson, Inorg. Chem., 18, 209 (1979). 16. J. H. Balthis, J. G. Bailar, Inorg. Synth., I , 123 (1939); M. R. Hatfield, Inorg. Synth., 3 , 148 (1950). 17. T. Golgotiv, I. Rosca, V. Petracovschi, Bull. Inst. Politch. lasi, 18, 21 (1972); Chem. Abstr., 79, 86925w (1973). 18. L. A. Nazarova, I. I. Chernyaev, A. S. Morozova, Zh. Neorg. Khim., 11, 2583 (1966). 19. S. N. Misra, T. N. Misra, R. C. Mehrotra, J . Inorg. Nucl. Chem., 25, 195 (1963). 20. T. N. Misra, Ph.D. thesis, Rajasthan University, Jaipur, 1963. 21. S. N. Misra, Ph.D. thesis, Rajasthan University, Jaipur, 1964. 22. M. J. Baillie, D. H. Brown, K. C. Moss, D. W. A. Sharp, J . Chem. Soc., A , 3110 (1968). 23. G. A. Razuvaev, V. N. Latyaeva, L. I. Vyshinskaya, Dokl. Akad. Nauk SSSR, 138, 1126 (1961); Chem. Abstr., 55, 27248b (1961). 24. A. N. Nesmeyanov, 0. V. Nogina, A. M. Berlin, A. S. Girshovich, G. V. Shatalov, I z c . Akad. Nauk SSSR, Otd. Khirn. Nauk, 2146 (1961); Chem. Abstr., 57, 11221f (1962). 25. R. B. King, R. N. Kapoor, J . Organomet. Chem., 15,457 (1968). 26. R. B. King, R. N. Kapoor, J . Inorg. Nucl. Chem., 31, 2169 (1969).
3.8.2.11 From Metal Atom and Related Reactions 3.8.2.11.1 Abstraction and Electron Transfer Processes
Transition metal atoms abstract oxygen from epoxides, including cyclohexene oxide1x2.Reaction efficiency, as measured by the amount of cyclohexene produced per metal atom, is Ti = 0.9, V = 2.8, Cr = 2.7, Co = 1.2, and Ni = 0.6: 0
0
+
M
4
0 +
[MO]
Chromium atoms abstract oxygen from 2,6-dimethylpyridine oxide, P h 3 P 0 , Me2S0, and nitro- and nitro~oarenes'-~.For nitro- and nitrosoarenes, nitrene or nitrenoid species are likely intermediates. Atoms of Ti, V, Cr, Co, and Ni also deoxygenate T H F and some ketones in low yield','. In addition, cyclohexanone can be reduced and coupled to 1,l'-bicyclohexyl 1,l'-diol by atoms of the early transition metals; the later transition metals are less reactive6. Iron atoms with ethylene oxide react with spontaneous C-0 insertion to form a matrix-isolated metallaoxetane7~*, Gas phase metal atom reactions, using high temperature, fast-flow reactors (HTFER), have been used in oxygen abstraction processes. The Fe 02-Fe0 0 mL/molg,". reaction at 1330°C proceeds with a rate coefficient of 3.6 x
+
+
(K. J. KLABUNDE)
1. 2. 3. 4. 5. 6. 7. 8. 9. 10.
J. Gladysz, J. Fulcher, S. Togashi, J . Org. Chem., 41, 3647 (1976). S. Togashi, J. G. Fulcher, B. R. Cho, M. Hasegawa, J. A. Gladysz, J . Org. Chem., 45,3044 (1980). J. Gladysz, J. Fulcher, S . Togashi, Tetrahedron Lett., 521 (1977). T. Chivers, P. L. Timms, J . Organomet. Chem., 118, C37 (1976). T. 0. Murdock, Ph.D. thesis, University of North Dakota, 1977. J. T. Miller, C. W. Dekock, J . Org. Chem., 46, 516 (1981). 2. Kafafi, R. H. Hauge, W. E. Billups, J. L. Margrave, J . Am. Chem. Soc., 109, 4775 (1987). 2. Kafafi, R. H. Hauge, 3. L. Margrave, J . Am. Chem. Soc., 107, 7550 (1985). A. Fontijn, S. C. Kurzius, J. J. Houghton, J. A. Emerson, Rea. Sci. Instrum., 43, 726 (1972). A. Fontijn, S. C. Kurzius, J. J. Houghton, Proc. Int. Symp. Combust., 14,167(1973); Chem. Abstr., 78, 62775a (1973).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
83 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 1 From Metal Atom and Related Reactions 3.8.2.1 1.3 Simple Orbital Mixing: Dioxygen and Carbon Dioxide with Metal Atoms 3.8.2.11.2. Oxidative Addition/Complexation Reactions
When C6FsBr oxidatively adds to Ni atoms, in the presence of toluene, the resultant C,F,-Ni-Br intermediate disproportionates and z-bonds to toluene yielding (C6F5)2Niq6-toluene’. The toluene ligand is displaced even by THF to yield synthetic amounts of stable etheratel:
Transition metal-oxygen bond formation by oxidative addition is illustrated in the combination of acid anhydrides with Pd atoms. Hexafluoroacetic anhydride codeposited with Pd forms an unstable complex, that reacts with PEt, yielding cis-bis(triethy1phosphine) perfluorodiacetatopalladium(II)2: 0
0
excess
0
0 - C - CF3
II
0 (K. J. KLABUNDE)
1. R. G. Gastinger, B. B. Anderson, K. J. Klabunde, J . Am. Chem. SOC.,102, 4959 (1980). 2. K. J. Klabunde, J. Y. F. Low, H. F. Efner, J . Am. Chem. SOC., 96, 1984 (1974). 3.8.2.11.3 Simple Orbital Mixing: Dioxygen and Carbon Dioxide with Metal Atoms
Transition metal atoms undergo microscale codeposition with 02,and the bonding of the resultant complexes is investigated spectroscopically (matrix isolation spectroscopy). Table 1 lists the complexes prepared, including some mixed complexes, along with comments about the interaction’ -4. This transition metal-02 interaction is side-on and does not involve 0-0 bond breakage under the low temperature conditions employed (generally 10-50 K). A stronger metal-02 interaction occurs when only one O2 is complexed and when heavier metals, (e.g., Pt and Rh) are employed. The N2 group causes the O2 to bind even more strongly, as shown by the lower IR vo=o values5. Iron atoms react with ethylene oxide;6 spontaneous C-0 insertion takes place to form a matrix-isolated metalla~xetane’,~. When Ti, V, Cr, Fe, Co, Ni, or Cu atoms are cocondensed with C 0 2 ,electron transfer followed by coupling occurs, and metal oxalates sometimes form. The efficiency of these reactions varies greatly. With Ti, V, and Cr, first insertion of the metal atom into a C-0 bond leads to an intermediate 0-M-CO species, which can react further with C027:
Ti
K + CO2-O=Ti-C=O 15
+ Ti=O + CEO + Ti-CEO
(a)
Similar schemes have been proposed for Cr and W atom reactions with C 0 2 / 0 2 8 , 9 .
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
83 3.8.2 Oxygen-Transition Metal and Oxygen-Inner Transition Metal Bond 3.8.2.1 1 From Metal Atom and Related Reactions 3.8.2.1 1.3 Simple Orbital Mixing: Dioxygen and Carbon Dioxide with Metal Atoms 3.8.2.11.2. Oxidative Addition/Complexation Reactions
When C6FsBr oxidatively adds to Ni atoms, in the presence of toluene, the resultant C,F,-Ni-Br intermediate disproportionates and z-bonds to toluene yielding (C6F5)2Niq6-toluene’. The toluene ligand is displaced even by THF to yield synthetic amounts of stable etheratel:
Transition metal-oxygen bond formation by oxidative addition is illustrated in the combination of acid anhydrides with Pd atoms. Hexafluoroacetic anhydride codeposited with Pd forms an unstable complex, that reacts with PEt, yielding cis-bis(triethy1phosphine) perfluorodiacetatopalladium(II)2: 0
0
excess
0
0 - C - CF3
II
0 (K. J. KLABUNDE)
1. R. G. Gastinger, B. B. Anderson, K. J. Klabunde, J . Am. Chem. SOC.,102, 4959 (1980). 2. K. J. Klabunde, J. Y. F. Low, H. F. Efner, J . Am. Chem. SOC., 96, 1984 (1974). 3.8.2.11.3 Simple Orbital Mixing: Dioxygen and Carbon Dioxide with Metal Atoms
Transition metal atoms undergo microscale codeposition with 02,and the bonding of the resultant complexes is investigated spectroscopically (matrix isolation spectroscopy). Table 1 lists the complexes prepared, including some mixed complexes, along with comments about the interaction’ -4. This transition metal-02 interaction is side-on and does not involve 0-0 bond breakage under the low temperature conditions employed (generally 10-50 K). A stronger metal-02 interaction occurs when only one O2 is complexed and when heavier metals, (e.g., Pt and Rh) are employed. The N2 group causes the O2 to bind even more strongly, as shown by the lower IR vo=o values5. Iron atoms react with ethylene oxide;6 spontaneous C-0 insertion takes place to form a matrix-isolated metalla~xetane’,~. When Ti, V, Cr, Fe, Co, Ni, or Cu atoms are cocondensed with C 0 2 ,electron transfer followed by coupling occurs, and metal oxalates sometimes form. The efficiency of these reactions varies greatly. With Ti, V, and Cr, first insertion of the metal atom into a C-0 bond leads to an intermediate 0-M-CO species, which can react further with C027:
Ti
K + CO2-O=Ti-C=O 15
+ Ti=O + CEO + Ti-CEO
(a)
Similar schemes have been proposed for Cr and W atom reactions with C 0 2 / 0 2 8 , 9 .
84
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond
3.8.3.1From Sulfur 3.8.3.1.I By Reaction with the Transition and Inner Transition Metal
TABLE 1. TRANSITION METAL-DIOXYGEN COMPLEXES STUDIED BY MATRIX ISOLATION SPECTROSCOPY Complexes
(cm-') 996 1062 977 912 1024 1111 927 1050 900 1045
a
Comments" Side-on Side-on vNZN 2243 cmvNXN 2260 cm-' Side-on Side-on Side-on Side-on Side-on Side-on
Point Group
Ref.
C2"
'
D2d Or D2h
C2"
D2d
c2, D2d
C2, D2d
Side-on refers to coordination mode
Vapors of some transition metal halides have been codeposited on microscale with 02'03": e.g., CrF2, MnF2, NiF2,and NiClz, which complex weakly with O2 (and NO) in a frozen Ar matrix. (K. J. KLABUNDE)
1. J. H. Darling, M. B. Garton-Sprenger, J. S. Ogden, J . Chem. Soc., Furaduy Trans. 2 (Symp)., 75 ( 1973). 2. D. McIntosh, G. A. Ozin, Inorg. Chem., 15, 2869 (1976). 3. H. Huber, G. A. Ozin, Can. J . Chem., 50, 3746 (1972). 4. H. Huber, W. Klotzbucher, G. A. Ozin, A. Vander Voet, Can. J . Chem., 51, 2722 (1973). 5. M. Moskovits, G. A. Ozin, in Cryochemistry, M. Moskovits, G. A. Ozin, eds., Wiley-Interscience, New York, 1976, pp. 261, 297. 6. L. A. Hanlan, G. A. Ozin, Inorg. Chem.., 16, 2848 (1977). 7. J. Mascetti, M. Tranquille, J . Phys. Chem., 29, 2177 (1988). 8. M. Almond, A. J. Dows, R. N. Perutz, Inorg. Chem., 24, 275 (1985). 9. M. Poliakoff, K. P. Smith, J. J. Turner, A. J. Wilkinson, J . Chem. SOC.,Dalton Trans., 651 (1982). 10. D. A. Van Leirsburg, C . W. Dekock, J . Phys. Chem., 78, 134 (1974). 11. C . W. Dekock, D. A. Van Leirsburg, J . Am. Chem. Soc., 94, 3235 (1972).
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.1 From Sulfur 3.8.3.1.1 By Reaction with the Transition and Inner Transition Metal
The transition and inner transition (lanthanide) elements react with sulfur to form sulfides'. Powdered Sc reacts with S at 1150°C under vacuum in a sealed quartz tube producing ScS. Stoichiometric quantities of the elements' form Y2S3. Heating powdered Ln elements with S produces nonhomogeneous mixtures containing Ln& and Ln2S4l. Heating these air-sensitive materials in vacuum to 1000°Cin a quartz tube produces pure LnS.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
84
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond
3.8.3.1From Sulfur 3.8.3.1.I By Reaction with the Transition and Inner Transition Metal
TABLE 1. TRANSITION METAL-DIOXYGEN COMPLEXES STUDIED BY MATRIX ISOLATION SPECTROSCOPY Complexes
(cm-') 996 1062 977 912 1024 1111 927 1050 900 1045
a
Comments" Side-on Side-on vNZN 2243 cmvNXN 2260 cm-' Side-on Side-on Side-on Side-on Side-on Side-on
Point Group
Ref.
C2"
'
D2d Or D2h
C2"
D2d
c2, D2d
C2, D2d
Side-on refers to coordination mode
Vapors of some transition metal halides have been codeposited on microscale with 02'03": e.g., CrF2, MnF2, NiF2,and NiClz, which complex weakly with O2 (and NO) in a frozen Ar matrix. (K. J. KLABUNDE)
1. J. H. Darling, M. B. Garton-Sprenger, J. S. Ogden, J . Chem. Soc., Furaduy Trans. 2 (Symp)., 75 ( 1973). 2. D. McIntosh, G. A. Ozin, Inorg. Chem., 15, 2869 (1976). 3. H. Huber, G. A. Ozin, Can. J . Chem., 50, 3746 (1972). 4. H. Huber, W. Klotzbucher, G. A. Ozin, A. Vander Voet, Can. J . Chem., 51, 2722 (1973). 5. M. Moskovits, G. A. Ozin, in Cryochemistry, M. Moskovits, G. A. Ozin, eds., Wiley-Interscience, New York, 1976, pp. 261, 297. 6. L. A. Hanlan, G. A. Ozin, Inorg. Chem.., 16, 2848 (1977). 7. J. Mascetti, M. Tranquille, J . Phys. Chem., 29, 2177 (1988). 8. M. Almond, A. J. Dows, R. N. Perutz, Inorg. Chem., 24, 275 (1985). 9. M. Poliakoff, K. P. Smith, J. J. Turner, A. J. Wilkinson, J . Chem. SOC.,Dalton Trans., 651 (1982). 10. D. A. Van Leirsburg, C . W. Dekock, J . Phys. Chem., 78, 134 (1974). 11. C . W. Dekock, D. A. Van Leirsburg, J . Am. Chem. Soc., 94, 3235 (1972).
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.1 From Sulfur 3.8.3.1.1 By Reaction with the Transition and Inner Transition Metal
The transition and inner transition (lanthanide) elements react with sulfur to form sulfides'. Powdered Sc reacts with S at 1150°C under vacuum in a sealed quartz tube producing ScS. Stoichiometric quantities of the elements' form Y2S3. Heating powdered Ln elements with S produces nonhomogeneous mixtures containing Ln& and Ln2S4l. Heating these air-sensitive materials in vacuum to 1000°Cin a quartz tube produces pure LnS.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 85 3.8.3.1 From Sulfur 3.8.3.1.2 By Reaction with Transition Metal and Inner Transition Metal Compounds
The elements Ti, Zr, and Hf react with S at 650°C in sealed, thick-walled Vycor tubes yielding MS2 and MS3. Upon thermal decomposition above 500"C, TiS3 yields Ti&; 800°C is required to form ZrSz and HfS23. The vanadium triad elements produce sulfide mixtures when combined in sealed 1000°C. The compounds V3S, VS, V&', and V2S3, Nbl + x S ~(not quartz tubes at NbS3), and Tal +xS3form. Regions of homogeneity exist for each binary sulfide. Formation of TaS2 and intercalation compounds are described4. Temperature and composition control must be enforced during preparation of each metal sulfide phase. Quartz tube high temperature (- 1000cC)syntheses yield CrS and WS2 from the elements'. When heated in an Fe tube, a stoichiometric mixture of Mo and S produces MoS2, material similar to the natural molybdenite mineral. The compound NaCrSz is prepared in a KNaC03 melt' at -1000°C in sealed quartz tubes. The compounds a-MnS', MnSZ6, and Re&' are readily formed. Pure FeS is obtained' from S using the sealed quartz tube technique at 1000°C.With KzCO3 present, KFeS3 forms's'. Both RuSz and OsSz form from the elements above 6OO0C9. The sulfides CoS and C0S2 form from stoichiometric quantities of the elements at 650°C in sealed quartz tubes'. Various RhS, phases form when Rh is heated with S up to 1100°C;the only compounds are Rh&, Rh&, Rh&, and Rh&'. When Ir burns in S, IrS is produced. At 900°C, in a sealed, evacuated quartz tube, stoichiometric quantities of Ni and S combine forming black P-NiS. Both PdS and PtS form when the powdered metal is heated with S. Both PdS2 and PtSz are obtained with excess S at temperatures above about 650°C. The phases Ni& and Pd4S also appear crystalline'. Other aspects of the formation of transition metal sulfides have been described'O~''.
-
(J. P. FACKLER, K. G. FACKLER) 1. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1125. 2. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 702. 3. L. E. Conroy, Inorg. Synth., 12, 158 (1970); 30, 22 (1995). 4. J. F. Revelli, Inorg. Synth., 19, 35 (1979). 5. H. Haraldsen, W. Klemna, 2.Anorg. Allg. Chem., 220, 271 (1936). 6. W. Biltz, F. Wiechmann, Anorg. Allg. Chem., 228, 271 (1936). 7. H. H. Murray, S. P. Kelty, R. R. Chianelli, Inorg. Chem., 33, 4418 (1994). 8. J. L. Deutsch, H. B. Jonassen, Inorg. Synth., 6, 170 (1960). 9. N. V. Sidgwick, Chemical Elements and Their compounds, Clarendon Press, Oxford, 1950 p. 1490. 10. J. D. Woolins, Encyclopedia Inorg. Chem., 7, 3954 (1994). 11. F. A. Cotton, G. Wilkinson, Adcances in Inorganic Chemistry, 5th ed., Wiley, New York, 1988.
3.8.3.1.2 By Reaction with the Transition Metal and Inner Transition Metal Compounds
Studies of the reaction of S (as opposed to polysulfides) with transition metal compounds deal primarily with metal sulfides; e.g., TiS2 (from Tic14 and HzS) when heated under pressure with S in a Vycor tube, produces TiS3'. Other phases such as Ti& and TiS are known'. Phase studies show broad homogeneity, ranging from ZrS1.6 to ZrSo.9 in the Zr-S system. Zr2S and Hf2S also are reported'. Metal-deficient sulfides of V, such as VS4, can be prepared by heating VzS3 with excess S. Other metal-deficient transition metal sulfides such as NbS3 or TaS2 are prepared similarly3.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 85 3.8.3.1 From Sulfur 3.8.3.1.2 By Reaction with Transition Metal and Inner Transition Metal Compounds
The elements Ti, Zr, and Hf react with S at 650°C in sealed, thick-walled Vycor tubes yielding MS2 and MS3. Upon thermal decomposition above 500"C, TiS3 yields Ti&; 800°C is required to form ZrSz and HfS23. The vanadium triad elements produce sulfide mixtures when combined in sealed 1000°C. The compounds V3S, VS, V&', and V2S3, Nbl + x S ~(not quartz tubes at NbS3), and Tal +xS3form. Regions of homogeneity exist for each binary sulfide. Formation of TaS2 and intercalation compounds are described4. Temperature and composition control must be enforced during preparation of each metal sulfide phase. Quartz tube high temperature (- 1000cC)syntheses yield CrS and WS2 from the elements'. When heated in an Fe tube, a stoichiometric mixture of Mo and S produces MoS2, material similar to the natural molybdenite mineral. The compound NaCrSz is prepared in a KNaC03 melt' at -1000°C in sealed quartz tubes. The compounds a-MnS', MnSZ6, and Re&' are readily formed. Pure FeS is obtained' from S using the sealed quartz tube technique at 1000°C.With KzCO3 present, KFeS3 forms's'. Both RuSz and OsSz form from the elements above 6OO0C9. The sulfides CoS and C0S2 form from stoichiometric quantities of the elements at 650°C in sealed quartz tubes'. Various RhS, phases form when Rh is heated with S up to 1100°C;the only compounds are Rh&, Rh&, Rh&, and Rh&'. When Ir burns in S, IrS is produced. At 900°C, in a sealed, evacuated quartz tube, stoichiometric quantities of Ni and S combine forming black P-NiS. Both PdS and PtS form when the powdered metal is heated with S. Both PdS2 and PtSz are obtained with excess S at temperatures above about 650°C. The phases Ni& and Pd4S also appear crystalline'. Other aspects of the formation of transition metal sulfides have been described'O~''.
-
(J. P. FACKLER, K. G. FACKLER) 1. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1125. 2. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 702. 3. L. E. Conroy, Inorg. Synth., 12, 158 (1970); 30, 22 (1995). 4. J. F. Revelli, Inorg. Synth., 19, 35 (1979). 5. H. Haraldsen, W. Klemna, 2.Anorg. Allg. Chem., 220, 271 (1936). 6. W. Biltz, F. Wiechmann, Anorg. Allg. Chem., 228, 271 (1936). 7. H. H. Murray, S. P. Kelty, R. R. Chianelli, Inorg. Chem., 33, 4418 (1994). 8. J. L. Deutsch, H. B. Jonassen, Inorg. Synth., 6, 170 (1960). 9. N. V. Sidgwick, Chemical Elements and Their compounds, Clarendon Press, Oxford, 1950 p. 1490. 10. J. D. Woolins, Encyclopedia Inorg. Chem., 7, 3954 (1994). 11. F. A. Cotton, G. Wilkinson, Adcances in Inorganic Chemistry, 5th ed., Wiley, New York, 1988.
3.8.3.1.2 By Reaction with the Transition Metal and Inner Transition Metal Compounds
Studies of the reaction of S (as opposed to polysulfides) with transition metal compounds deal primarily with metal sulfides; e.g., TiS2 (from Tic14 and HzS) when heated under pressure with S in a Vycor tube, produces TiS3'. Other phases such as Ti& and TiS are known'. Phase studies show broad homogeneity, ranging from ZrS1.6 to ZrSo.9 in the Zr-S system. Zr2S and Hf2S also are reported'. Metal-deficient sulfides of V, such as VS4, can be prepared by heating VzS3 with excess S. Other metal-deficient transition metal sulfides such as NbS3 or TaS2 are prepared similarly3.
86
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.1 Substitution Reactions Transition and Inner Transition Metal
The affinity of Mo and W for S makes possible the formation of MoS2 and WSz from the oxides': Moo2 3sMS2 SO2 (a)
+
wo3
+ 7s-
+
2wsz
3so2
(b)
(J. P. FACKLER, K. G. FACKLER)
1. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1222; L. E. Conroy, Inorg. Synth., 30, 22 (1995). 2. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 702. 3. F. Jellinek, in Inorganic SuEfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 705.
3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.1 By Substitution Reactions with Transition Metal and inner Transition Metal Compounds
Reaction of HzS with oxides, halides, and other compounds of transition and lanthanide metals is the most convenient method for preparing the sulfides'. Anhydrous chlorides of Sc, Y, and the lanthanides react with dry HIS producing sesquisulfides, M2S31'2. The initial reaction temperature of 500-700°C is raised to 800-1500°C (in a quartz tube) before the materials are cooled in a stream of H2S. Anhydrous M2(S04)3 yields polysulfides and oxosulfidesl under similar conditions. From Eu203, black crystalline EuS forms3: Starting with the Ti triad metal tetrachloride^'^^, a tube furnace reaction with HzS at 600°C yields Ti&, ZrSz, and HfSz. Metal-deficient sulfides form upon further heating with S to temperatures near 800°C. Sulfur is lost from the compounds near lOOO"C, yielding various sulfur-poor derivatives. In the presence' of C, H2S reacts with the HfOz forming HfS2: HfS2 2Hz + 2CO HfO2 2C 2HzS(b)
+
+
+
Oxides of the vanadium triad elements, M205, react with H2S in a CSz-saturated stream at 700-1300°C to produce sulfides. Product compositions' are close to VzS3 (vs1.47),NbS1.74, and TaSz.0. Thermal decomposition of vZs3 (which also can be formed from V 2 0 3 with H2S) produces VS. Thermal decomposition of (NH4)3VS4 produces VS2. Salts of pentavalent V, Nb, and Ta containing the anion [MS413- are known6. Stoichiometric Cr& is formed by allowing CrC13 in a H2S stream to react at 600-650°C. Treatment of an ammoniacal (NH&M07024 solution with H2S yields (NH&MoS4, a compound studied because of its biological relevance'. The (NH4)2WS4 also is formed from ammoniacal H2S solutions'. Various added bivalent metal ions such as M' = Zn, Ni, Fe, Co, Pd, and Pt result in formation of complexes of the type [M'(S2MS&]"-, n = 2 generally, but also n = 3 for M' = Fe form from (NH&MS4. Cations such as [(CzH5)4N] + produce crystalline salts of these complex anions'. At RT, [MoCl(NNMe2)2 (PPh3)z]Cl reacts with [ B u ~ ~ N ] ~ Mino MeCN S~ formingg the dark green, dichroic SzMoS2Mo(NNMez)zPPh3. Reactions of [MS4lZ(M = Mo, W) with various species in weakly coordinating solvents such as acetone, CHzCl2, etc., are described in Figure 1.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 86
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.1 Substitution Reactions Transition and Inner Transition Metal
The affinity of Mo and W for S makes possible the formation of MoS2 and WSz from the oxides': Moo2 3sMS2 SO2 (a)
+
wo3
+ 7s-
+
2wsz
3so2
(b)
(J. P. FACKLER, K. G. FACKLER)
1. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1222; L. E. Conroy, Inorg. Synth., 30, 22 (1995). 2. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 702. 3. F. Jellinek, in Inorganic SuEfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 705.
3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.1 By Substitution Reactions with Transition Metal and inner Transition Metal Compounds
Reaction of HzS with oxides, halides, and other compounds of transition and lanthanide metals is the most convenient method for preparing the sulfides'. Anhydrous chlorides of Sc, Y, and the lanthanides react with dry HIS producing sesquisulfides, M2S31'2. The initial reaction temperature of 500-700°C is raised to 800-1500°C (in a quartz tube) before the materials are cooled in a stream of H2S. Anhydrous M2(S04)3 yields polysulfides and oxosulfidesl under similar conditions. From Eu203, black crystalline EuS forms3: Starting with the Ti triad metal tetrachloride^'^^, a tube furnace reaction with HzS at 600°C yields Ti&, ZrSz, and HfSz. Metal-deficient sulfides form upon further heating with S to temperatures near 800°C. Sulfur is lost from the compounds near lOOO"C, yielding various sulfur-poor derivatives. In the presence' of C, H2S reacts with the HfOz forming HfS2: HfS2 2Hz + 2CO HfO2 2C 2HzS(b)
+
+
+
Oxides of the vanadium triad elements, M205, react with H2S in a CSz-saturated stream at 700-1300°C to produce sulfides. Product compositions' are close to VzS3 (vs1.47),NbS1.74, and TaSz.0. Thermal decomposition of vZs3 (which also can be formed from V 2 0 3 with H2S) produces VS. Thermal decomposition of (NH4)3VS4 produces VS2. Salts of pentavalent V, Nb, and Ta containing the anion [MS413- are known6. Stoichiometric Cr& is formed by allowing CrC13 in a H2S stream to react at 600-650°C. Treatment of an ammoniacal (NH&M07024 solution with H2S yields (NH&MoS4, a compound studied because of its biological relevance'. The (NH4)2WS4 also is formed from ammoniacal H2S solutions'. Various added bivalent metal ions such as M' = Zn, Ni, Fe, Co, Pd, and Pt result in formation of complexes of the type [M'(S2MS&]"-, n = 2 generally, but also n = 3 for M' = Fe form from (NH&MS4. Cations such as [(CzH5)4N] + produce crystalline salts of these complex anions'. At RT, [MoCl(NNMe2)2 (PPh3)z]Cl reacts with [ B u ~ ~ N ] ~ Mino MeCN S~ formingg the dark green, dichroic SzMoS2Mo(NNMez)zPPh3. Reactions of [MS4lZ(M = Mo, W) with various species in weakly coordinating solvents such as acetone, CHzCl2, etc., are described in Figure 1.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 87 3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.1 Substitution Reactions Transition and Inner Transition Metal
Fe(SPh),z-
Fe(S,COR),- I
[Fe(S,MS,),I'-
J
(M = W)
Figure 1. Reaction of the [MS4I2- anions of Mo and W7
Figure 2. Two isomers of [Mo2S,2l2-.
Several products form upon addition of S or polysulfides to [MoS4I2-. One characterized species, [Mo2Sl2l2- contains either MS2 or MS4 chelate rings depending on the method of formation"*" (see Fig. 2). Organometallic compounds of the type ( V ~ - C ~ H ~ )(M ~M ~ , W) also contain MS4 ringsI2. =S Mo, Reaction of (n5-C5Hs)2Mo(C0)3and its Cs(Me)s analogue with S produces hydrocarbon-insoluble product^'^. When slurried with degassed CHC13 under 1 atm H2. H2S forms along with purple-black crystals of [C5HsMo(S)SH]2, which react with RSH in CHC13/toluene yielding [CsHsMo(S)SR]2 (1).
88 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.1 Substitution Reactions Transition and Inner Transition Metal
1 Reaction of H2S with MoOz(S’CNRz), R = C3H7, in acetone produces Mo species including M o ~ S ~ ( S ~ C N R and & MoO(S2)(SzCNR2)2, a species containing a chelating Sz ligandI4. The bridging SH and SR groups undergo exchange with olefins and acetylenes. From a boiling 50% NH3 solution of MnClz containing some K2C204, the a modification of MnS precipitates with H2S. The y modification precipitates under slightly different conditions’. The black sulfide Re’s7 is obtained from [ReO4]- in 10% HCl upon saturation with HzS1.’5. The cluster anions [Fe&(SR)4]’and [Fe2Sz(SR)2]’- are synthesized16 from Fe(II1) thiolates, H2S, and NaOCH3. A convenient synthesis from RSH, FeC13, and S exist^'^. There are mixed Fe, Mo, S clusters such as [ M z F ~ ~ S E ( S R )(M ~ ~=] Mo, ~ - W)”. Starting with easily prepared divalent metal xanthates M(S2COR)2, the anions [M(SR)4I2- (M = Fe, Co, Mn, Zn, Cd) can formIg. Also, [Fe2S4(SR)4I2- is prepared conveniently from [Fe(SR)4I2-. A broad review” of metal chalcogenide cluster syntheses and their general structural types, including tables of procedures used to form MZto Mlo compounds, describes eight general synthetic methods. Clear drawings are presented, and larger megaclusters (to C U ~ O are) included. Coverage is comprehensive and includes some information about chalcogenide colloids and bioinorganic metal-sulfur clusters. A rare example of H2S coordinated directly to a metal, [(NH~)~RU(SHZ)]~’, is obtained’’ by reacting HzS with [(NH~)~RU(OHZ)]”. Both CoS and NiS precipitate1 from aqueous solutions of the metal ions with H2S. The apparatus used should be purged with 02-free and COz-free N2. The dried sulfide can be reacted with stoichiometric amounts of S to form S-rich products (e.g., COSZ, NiS2, c03s4, Co&). A dark brown precipitate of PtS2, slightly soluble in alkali sulfide solutions, forms when H2S is passed through a hot H2PtC16 solution’. However, from ammoniacal solutions of H2S containing S (which contain Sz -), (NH4)2PtS15precipitates. Crystalline [(C3H7)4N]2PtS15,which contains MS5 rings”, can be reduced to [(C3H7)4N]2Pt(S5)2 with KCN. Rhodium displays similar chemistry”. NasRhCl6
+ 3(NH&S5
-
(NH&Rh(S5)3
+ 3NaC1 + 3NH4Cl
(4
In contrast, with Pd, (NH4)2PdS11 , a species containing nonchelated s6 chains linking metal atoms, forms. Reacting (diphos)MClZ [M = Ni, Pd, or Pt, (diphos) = ethylene bis(dipheny1phosphane)l in EtOH” with Na& produces (diphos)MS4. The Pt complex also is obtained by S abstraction from Pt(S5):- with a phosphine”. Whereas H2S reacts with bis(diph0s)halides of Pd and Pt forming (diphos)M(SH)z, NaSH in EtOH/benzene is required for formation of the analogous Ni complex”. With triphosphine amine ligands, nP3, dimers of the type [(P3)NiSNi(P3)]BF4 and
89 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.2 By Insertion of Sulfur into Transition and Inner Transition Metal-Ligand
(P3)CoSCo(P3) are preparedz3. The trigonal-bipyramidal derivatives (nP3)NiSH containing Ni(1) form from [Ni(nP3)]. The VO’+-containing species reacts with B2S3 forming VS” products24.Various VOL’ species, where L is a chelate ligand such as acetylacetone or its derivatives, react with B’S3 in MeOH at reflux to produce crystalline VSLl. Presumably this technique will find wide applicability throughout the transition and inner transition series for 0 replacement by S. (J. P. FACKLER, K. G. FACKLER) 1. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1466. 2. A. W. Sleight, D. P. Kelly, Inorg. Synth., 14, 152 (1973); 30, 20 (1995). 3. R. D. Archer, N. Mitchell, Inorg. Synth., 10, 77 (1967). 4. R. C. Hall, J. P. Mickel, Inorg. Synth., 5, 82 (1957). 5. B. T. Kaminskii, G. N. Prokofleva, A. S. Plygunov, P. A. Galitskii, Porosh. Met., 7, 6 (1973); Chem. Abstr., 80, 5305 (1974). 6. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 708. 7. R. H. Holm, Adc. Inorg. Chem., 38, 1, (1992); D. Coucouvanis, Ace. Chem. Res., 24, 1 (1991). 8. E. Diemann, A. Miiller, Coord. Chem. Rev., 10, 79 (1973); A. Miiller, E. Diemann, Cornp. Coord. Chem., 2, 515 (1987). 9. J. R. Dilworth, J. A. Zubieta, J . Chem. Soc., Chem. Commun., 132 (1981). 10. A. Muller, W. 0. Nolte, B. Krebs, Angew. Chem., Int. Ed. Engl., 17, 279 (1978). 11. A. I. Hadjikyriacou, D. Coucouvanis, Inorg. Synth., 27, 39 (1990); D. Coucouvanis, P. R. Patil, M. G. Kanatzidis, N. C. Baenziger, Inorg. Chem., 24, 24 (1985). 12. M. Schmitt, G. G. Hoffman, Z . Naturforsch., Teil B, 34C, 451 (1979). 13. L. C. Hurd, E. Brimor, Inorg. Synth., I , 177 (1939). 14. J. Dirand, L. Ricard, R. Weiss, Inorg. Nuclear Chem. Lett., 11, 661 (1975). 15. L. C. Hurd, E. Brimor, Inorg. Synth., 1, 177 (1939). 16. R. H. Holm, Acc. Chem. Res., 10, 427 (1977). 17. G. Christou, C. David Garner, A. Balasubramanian, B. Ridge, H. N. Rydon, Inorg. Synth.,21,33 (1984). 18. T. E. Woff, P. P. Power, R. E. Frankel, R. H. Holm, J . Am. Chem. Soc., 102, 4694 (1980). 19. D. Coucouvanis, C. N. Murphy, E. Simhon, P. Stremple, M. Draganjac, Inorg. Synth., 21, 23 20. 21. 22. 23. 24.
(1982).
I. Dance, K. Fisher, Prog. Inorg. Chem., 41, 637 (1994). C. Kuehn, S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980). R. A. Krause, J. L. Cronin, Inorg. Synth., 21, 12 (1982). C. Mealli, S. Midolline, L. Sacconi, Inorg. Chem., 17, 632 (1978). K. P. Callahan, P. J. Durand, Inorg. Chem., 19, 3211 (1980).
3.8.3.2.2 By Insertion of Sulfur into Transition and Inner Transition Metal-Ligand Bonds
Since the first report’ of sulfur addition to an Ni(SzCR2)to form Ni(SzCR)(S3CR), several related perthio species’, including the Pd, Pt, and Fe derivatives, have been formed and studied: Os(S,CR),
+8 0
S8
-
M(S2CR),-,(S,CR),
(a)
Both aliphatic and aromatic R groups allow S-atom insertion. With 0 s it is possible to isolate a dithiocarbamate derivative (R = NRJ3:
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
89 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.2 From Hydrogen Sulfide, Polysulfides, and Thiols 3.8.3.2.2 By Insertion of Sulfur into Transition and Inner Transition Metal-Ligand
(P3)CoSCo(P3) are preparedz3. The trigonal-bipyramidal derivatives (nP3)NiSH containing Ni(1) form from [Ni(nP3)]. The VO’+-containing species reacts with B2S3 forming VS” products24.Various VOL’ species, where L is a chelate ligand such as acetylacetone or its derivatives, react with B’S3 in MeOH at reflux to produce crystalline VSLl. Presumably this technique will find wide applicability throughout the transition and inner transition series for 0 replacement by S. (J. P. FACKLER, K. G. FACKLER) 1. G. Brauer, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1466. 2. A. W. Sleight, D. P. Kelly, Inorg. Synth., 14, 152 (1973); 30, 20 (1995). 3. R. D. Archer, N. Mitchell, Inorg. Synth., 10, 77 (1967). 4. R. C. Hall, J. P. Mickel, Inorg. Synth., 5, 82 (1957). 5. B. T. Kaminskii, G. N. Prokofleva, A. S. Plygunov, P. A. Galitskii, Porosh. Met., 7, 6 (1973); Chem. Abstr., 80, 5305 (1974). 6. F. Jellinek, in Inorganic Sulfur Chemistry, G. Nickless, ed., Elsevier, New York, 1968, p. 708. 7. R. H. Holm, Adc. Inorg. Chem., 38, 1, (1992); D. Coucouvanis, Ace. Chem. Res., 24, 1 (1991). 8. E. Diemann, A. Miiller, Coord. Chem. Rev., 10, 79 (1973); A. Miiller, E. Diemann, Cornp. Coord. Chem., 2, 515 (1987). 9. J. R. Dilworth, J. A. Zubieta, J . Chem. Soc., Chem. Commun., 132 (1981). 10. A. Muller, W. 0. Nolte, B. Krebs, Angew. Chem., Int. Ed. Engl., 17, 279 (1978). 11. A. I. Hadjikyriacou, D. Coucouvanis, Inorg. Synth., 27, 39 (1990); D. Coucouvanis, P. R. Patil, M. G. Kanatzidis, N. C. Baenziger, Inorg. Chem., 24, 24 (1985). 12. M. Schmitt, G. G. Hoffman, Z . Naturforsch., Teil B, 34C, 451 (1979). 13. L. C. Hurd, E. Brimor, Inorg. Synth., I , 177 (1939). 14. J. Dirand, L. Ricard, R. Weiss, Inorg. Nuclear Chem. Lett., 11, 661 (1975). 15. L. C. Hurd, E. Brimor, Inorg. Synth., 1, 177 (1939). 16. R. H. Holm, Acc. Chem. Res., 10, 427 (1977). 17. G. Christou, C. David Garner, A. Balasubramanian, B. Ridge, H. N. Rydon, Inorg. Synth.,21,33 (1984). 18. T. E. Woff, P. P. Power, R. E. Frankel, R. H. Holm, J . Am. Chem. Soc., 102, 4694 (1980). 19. D. Coucouvanis, C. N. Murphy, E. Simhon, P. Stremple, M. Draganjac, Inorg. Synth., 21, 23 20. 21. 22. 23. 24.
(1982).
I. Dance, K. Fisher, Prog. Inorg. Chem., 41, 637 (1994). C. Kuehn, S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980). R. A. Krause, J. L. Cronin, Inorg. Synth., 21, 12 (1982). C. Mealli, S. Midolline, L. Sacconi, Inorg. Chem., 17, 632 (1978). K. P. Callahan, P. J. Durand, Inorg. Chem., 19, 3211 (1980).
3.8.3.2.2 By Insertion of Sulfur into Transition and Inner Transition Metal-Ligand Bonds
Since the first report’ of sulfur addition to an Ni(SzCR2)to form Ni(SzCR)(S3CR), several related perthio species’, including the Pd, Pt, and Fe derivatives, have been formed and studied: Os(S,CR),
+8 0
S8
-
M(S2CR),-,(S,CR),
(a)
Both aliphatic and aromatic R groups allow S-atom insertion. With 0 s it is possible to isolate a dithiocarbamate derivative (R = NRJ3:
90 3.8 Formation of Bonds between the Group VIB Elements
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.3 Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
An Re derivative, [Re2(p-SS2CN(CH3)2)2(S2CN(CH3)2)3] [S03CF3], also has been characterized4. Isolation and characterization of Ni3(S2CR)3(S3CR),a species containing trithioorthoacetate', by reaction of Ni(S2CR), with CS2 in EtOH, supports mass spectroscopic data6 indicating that S insertion occurs at the C atom of the ligands. The best-known S insertion reactions occur with metal cyanide complexes'. The thiocyanates produced are either S- or N-bonded to the metal, depending on the metal ion and other ligands present. Similar reactions of metal-phosphine complexes, MPR3, producing metal phosphine sulfide derivatives, MSPR3, are less well studied. (J. P. FACKLER, K. G. FACKLER)
D. Coucouvanis, J. P. Fackler, Jr., J . Am. Chem. Soc., 89, 1346 (1967). D. Coucouvanis, Prog. Inorg. Chem., 26, 301 (1979). L. J. Maheu, L. H. Pignolet, J . Am. Chem. SOC.,102, 6347 (1980). L. Wei, T. R. Halbert, H. H. Murray, 111, E. I. Stiefel, J . Am. Chem. SOC.,I I 2 , 6431 (1990). M. Bonamico, G. Dessy, V. Fares, J . Chem. SOC., Dalton Trans., 2954 (1975). J. P. Fackler, Jr., J. A. Fetchin, J. A. Smith, J . Am. Chem. Soc., 92, 2910 (1970); J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. SOC.,94, 7323 (1972). 7. J. L. Burmeister, in The Chemistry and Biochemistry of Thiocyanic Acid and I t s Dericatices, A. A. Newman, ed., Academic Press, London, 1975, p. 68; A. H. Norbury, Adc. Inorg. Chem. Radiochem., 17, 231 (1975).
1. 2. 3. 4. 5. 6.
3.8.3.2.3 By Oxidation of the Transition Metal and Inner Transition Metal Complexes
Photolysis of W(CO)6 in pentane while H2S is bubbled through the solution leads' to molecular H2S coordination, W(CO),(H2S).Some SH species, e.g. (q5-C5H5)2Ti(SH)z are produced by oxidation of and Pt [P(C6H5)3]2H(SH)or (q5-C5H5)Ni(P(C4H9)3SH, lower valent species.
Refluxing [(q5-CSH5)Fe(C0)2]2with (Et),S2 in methylcyclohexane forms [ q 5 CSH5-Fe(CO)SC2HS]2. Reflux of this complex with S produces (qS-CSH5)2Fe2(S2)(Et)2. The (q5-C5H5)4Fe4S6 cluster also is formed from the carbonyl dime?. (J. P. FACKLER, K. G. FACKLER)
1. C. Kuehn and S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980); A. Muller, E. Diemann, Comp. Coord. Chem., 2, 515 (1987). 2. G. J. Kubas, P. J. Vergamini, Inorg. Synth., 21, 37 (1981).
3.8.3.3 From Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
Some of the first thioether complexes' were formed with the less reactive elements, Pt(SR2)2C12and MC13(SR2)3(M = Rh; Ir, Ru) by substitution of aquo or amine complexes2:
There are organometallic complexes containing bridging thioether ligands'. Complexes of [S(Me)3]+, [(NH3)5R~S(Me)3]PF2,and [(q5-C5H5)Mn(C0)2 S(Me)3]BF4 are known', the latter forms by alkylation of the coordinated thio ether. Thioalkylation of a chelate-coordinated thiol is also achieved3.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
90 3.8 Formation of Bonds between the Group VIB Elements
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.3 Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
An Re derivative, [Re2(p-SS2CN(CH3)2)2(S2CN(CH3)2)3] [S03CF3], also has been characterized4. Isolation and characterization of Ni3(S2CR)3(S3CR),a species containing trithioorthoacetate', by reaction of Ni(S2CR), with CS2 in EtOH, supports mass spectroscopic data6 indicating that S insertion occurs at the C atom of the ligands. The best-known S insertion reactions occur with metal cyanide complexes'. The thiocyanates produced are either S- or N-bonded to the metal, depending on the metal ion and other ligands present. Similar reactions of metal-phosphine complexes, MPR3, producing metal phosphine sulfide derivatives, MSPR3, are less well studied. (J. P. FACKLER, K. G. FACKLER)
D. Coucouvanis, J. P. Fackler, Jr., J . Am. Chem. Soc., 89, 1346 (1967). D. Coucouvanis, Prog. Inorg. Chem., 26, 301 (1979). L. J. Maheu, L. H. Pignolet, J . Am. Chem. SOC.,102, 6347 (1980). L. Wei, T. R. Halbert, H. H. Murray, 111, E. I. Stiefel, J . Am. Chem. SOC.,I I 2 , 6431 (1990). M. Bonamico, G. Dessy, V. Fares, J . Chem. SOC., Dalton Trans., 2954 (1975). J. P. Fackler, Jr., J. A. Fetchin, J. A. Smith, J . Am. Chem. Soc., 92, 2910 (1970); J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. SOC.,94, 7323 (1972). 7. J. L. Burmeister, in The Chemistry and Biochemistry of Thiocyanic Acid and I t s Dericatices, A. A. Newman, ed., Academic Press, London, 1975, p. 68; A. H. Norbury, Adc. Inorg. Chem. Radiochem., 17, 231 (1975).
1. 2. 3. 4. 5. 6.
3.8.3.2.3 By Oxidation of the Transition Metal and Inner Transition Metal Complexes
Photolysis of W(CO)6 in pentane while H2S is bubbled through the solution leads' to molecular H2S coordination, W(CO),(H2S).Some SH species, e.g. (q5-C5H5)2Ti(SH)z are produced by oxidation of and Pt [P(C6H5)3]2H(SH)or (q5-C5H5)Ni(P(C4H9)3SH, lower valent species.
Refluxing [(q5-CSH5)Fe(C0)2]2with (Et),S2 in methylcyclohexane forms [ q 5 CSH5-Fe(CO)SC2HS]2. Reflux of this complex with S produces (qS-CSH5)2Fe2(S2)(Et)2. The (q5-C5H5)4Fe4S6 cluster also is formed from the carbonyl dime?. (J. P. FACKLER, K. G. FACKLER)
1. C. Kuehn and S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980); A. Muller, E. Diemann, Comp. Coord. Chem., 2, 515 (1987). 2. G. J. Kubas, P. J. Vergamini, Inorg. Synth., 21, 37 (1981).
3.8.3.3 From Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
Some of the first thioether complexes' were formed with the less reactive elements, Pt(SR2)2C12and MC13(SR2)3(M = Rh; Ir, Ru) by substitution of aquo or amine complexes2:
There are organometallic complexes containing bridging thioether ligands'. Complexes of [S(Me)3]+, [(NH3)5R~S(Me)3]PF2,and [(q5-C5H5)Mn(C0)2 S(Me)3]BF4 are known', the latter forms by alkylation of the coordinated thio ether. Thioalkylation of a chelate-coordinated thiol is also achieved3.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
90 3.8 Formation of Bonds between the Group VIB Elements
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.3 Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
An Re derivative, [Re2(p-SS2CN(CH3)2)2(S2CN(CH3)2)3] [S03CF3], also has been characterized4. Isolation and characterization of Ni3(S2CR)3(S3CR),a species containing trithioorthoacetate', by reaction of Ni(S2CR), with CS2 in EtOH, supports mass spectroscopic data6 indicating that S insertion occurs at the C atom of the ligands. The best-known S insertion reactions occur with metal cyanide complexes'. The thiocyanates produced are either S- or N-bonded to the metal, depending on the metal ion and other ligands present. Similar reactions of metal-phosphine complexes, MPR3, producing metal phosphine sulfide derivatives, MSPR3, are less well studied. (J. P. FACKLER, K. G. FACKLER)
D. Coucouvanis, J. P. Fackler, Jr., J . Am. Chem. Soc., 89, 1346 (1967). D. Coucouvanis, Prog. Inorg. Chem., 26, 301 (1979). L. J. Maheu, L. H. Pignolet, J . Am. Chem. SOC.,102, 6347 (1980). L. Wei, T. R. Halbert, H. H. Murray, 111, E. I. Stiefel, J . Am. Chem. SOC.,I I 2 , 6431 (1990). M. Bonamico, G. Dessy, V. Fares, J . Chem. SOC., Dalton Trans., 2954 (1975). J. P. Fackler, Jr., J. A. Fetchin, J. A. Smith, J . Am. Chem. Soc., 92, 2910 (1970); J. P. Fackler, Jr., J. A. Fetchin, D. C. Fries, J . Am. Chem. SOC.,94, 7323 (1972). 7. J. L. Burmeister, in The Chemistry and Biochemistry of Thiocyanic Acid and I t s Dericatices, A. A. Newman, ed., Academic Press, London, 1975, p. 68; A. H. Norbury, Adc. Inorg. Chem. Radiochem., 17, 231 (1975).
1. 2. 3. 4. 5. 6.
3.8.3.2.3 By Oxidation of the Transition Metal and Inner Transition Metal Complexes
Photolysis of W(CO)6 in pentane while H2S is bubbled through the solution leads' to molecular H2S coordination, W(CO),(H2S).Some SH species, e.g. (q5-C5H5)2Ti(SH)z are produced by oxidation of and Pt [P(C6H5)3]2H(SH)or (q5-C5H5)Ni(P(C4H9)3SH, lower valent species.
Refluxing [(q5-CSH5)Fe(C0)2]2with (Et),S2 in methylcyclohexane forms [ q 5 CSH5-Fe(CO)SC2HS]2. Reflux of this complex with S produces (qS-CSH5)2Fe2(S2)(Et)2. The (q5-C5H5)4Fe4S6 cluster also is formed from the carbonyl dime?. (J. P. FACKLER, K. G. FACKLER)
1. C. Kuehn and S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980); A. Muller, E. Diemann, Comp. Coord. Chem., 2, 515 (1987). 2. G. J. Kubas, P. J. Vergamini, Inorg. Synth., 21, 37 (1981).
3.8.3.3 From Thioethers, Organic Polysulfides, and Other Sulfur Donor Ligands
Some of the first thioether complexes' were formed with the less reactive elements, Pt(SR2)2C12and MC13(SR2)3(M = Rh; Ir, Ru) by substitution of aquo or amine complexes2:
There are organometallic complexes containing bridging thioether ligands'. Complexes of [S(Me)3]+, [(NH3)5R~S(Me)3]PF2,and [(q5-C5H5)Mn(C0)2 S(Me)3]BF4 are known', the latter forms by alkylation of the coordinated thio ether. Thioalkylation of a chelate-coordinated thiol is also achieved3.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 91 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.1 By Oxidation of the Metals and Their Complexes
+
[(en)’ C O S C H ~ C H ~ N H ~ ]C6H4(C0)’NSR ’~
2 [(en)2CoS(SR)CH2CH2NHz]3++ [F3BN(C0)2C6H4]
(b)
Dithio and cyclic polythio ether complexes1 are produced by substitution reactions on metal complexes with the preformed sulfur ligand4. (J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4.
C. G. Kuehn, S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980). B. R. James; F. T. Ng, J . Chcm. Soc., Dalton Trans., 1321 (1972). D. L. Nosco, R. C. Elder, E. Deutsch, Inorg. Chem., 19, 2545 (1980). A. J. Blake, R. 0. Gould, A. J. Holder, T. I. Hyde, M. Schroder, Polyhedron, 8, 513 (1989); A. J. Blake, R. 0. Gould, A. J. Holder, T. I. Hyde, M. Schroder, J . Chem. Soc., Dalton Trans., 1759 (1990); A. Miiller, Comp. Coord. Chem., 2, 551 (1987).
3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates, and Other 1,l-Dithio Compounds (See 3.7.3, Table 1) 3.8.3.4.1 By Oxidation of the Metals and Their Complexes
Oxidation of low valent transition metal complexes with 1,l-dithio disulfides can yield 1,l-dithiolate derivatives’: 2C0(11)
+ 3(R,NC(S)S), +2Co(S2CNR2)3
(a)
Similarly, [M(S2CNR2)3]X,where M = Ni, Pd, and Pt and X = halogen, by oxidation of M(S2CNR& species with halogens or by oxidation of the M(SzCNR2)2X2complexes with (R2NCS2)2.Metal carbonyls are oxidized with (RzNCS2)’and dixanthogen. The eight-coordinated Mo [S2CN(C2H5)2]4forms by this procedure4. Oxidation of Fe(S2CNR2)2with N O produces3 Fe(S2CNR2)2N0, a squarepyramidal complex with nearly linear FeNO bonding5. Further oxidation5 with X2 (X = I, Br, SCN) or NOz gives six-coordinated products such as ONFe(S2CNR&X. Electrochemical oxidation of R u ( S ~ C N R ~yields )~ various cations6 such as RuZ[SzCN(Me)2]l. One of the more remarkable oxidations observed is formation of Ni [ S , C N ( ~ - B U ),C1 ~ ] from Ni [S2CN(n-Bu)J2 on reaction with excess ZnC1, in peroxide-free EtzO under anaerobic conditions’. This reaction is undoubtedly associated with the electron-pair acceptor acidity of Zn halides and the ease of forming oxidized species such as [R2NCS2CSNRzl2’ by loss of S. Etherates of BF3 oxidize Fe(S2CNRJ3 to Fe(S2CNR2)3BF4. A similar reaction with R u ( S ~ C N R ’ ) ~produces cation [RU~(S~CNR ) ~ ] [ C O ~ ( S ~ C N R ~ ) ~forms7 +.~Also, ] B F ~from reaction of BF3 with Co(SZCNRJ3. Thiuram monosulfide, [(R,NC(S)],S, is used as an oxidant forming’ Fe(SzCNR2)2C1from FeCI,. (J. P. FACKLER, K. G. FACKLER) 1. D. Coucouvanis, Prog. Inorg. Chem., 11, 233 (1970) 2. J. Willemse, J. A. Cras, J. J. Steggerda, C. P. Keijzers, Struct. Bond. (Berlin),28, 83 (1976); J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 3. J. P. Fackler, Jr., Prog. Inorg. Chern., 21, 23 (1976). 4. R. P. Burns, F. P. McCullough, C. A. McAuliffe, Adc. Inorg. Clzem. Radiochem., 26, 301 (1979). 5. D. Coucouvanis, Prog. Inorg. Chem., 26, 301 (1979). 6. A. R. Hendrickson, J. M. Hope, R. L. Martin, J . Chem. Soc., Dalton Trans., 2032 (1976). 7. L. H. Pignolet, B. M. Mattson, J . Chenz. Soc., Chem. Commun., 49 (1975).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 91 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.1 By Oxidation of the Metals and Their Complexes
+
[(en)’ C O S C H ~ C H ~ N H ~ ]C6H4(C0)’NSR ’~
2 [(en)2CoS(SR)CH2CH2NHz]3++ [F3BN(C0)2C6H4]
(b)
Dithio and cyclic polythio ether complexes1 are produced by substitution reactions on metal complexes with the preformed sulfur ligand4. (J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4.
C. G. Kuehn, S. S. Isied, Prog. Inorg. Chem., 27, 153 (1980). B. R. James; F. T. Ng, J . Chcm. Soc., Dalton Trans., 1321 (1972). D. L. Nosco, R. C. Elder, E. Deutsch, Inorg. Chem., 19, 2545 (1980). A. J. Blake, R. 0. Gould, A. J. Holder, T. I. Hyde, M. Schroder, Polyhedron, 8, 513 (1989); A. J. Blake, R. 0. Gould, A. J. Holder, T. I. Hyde, M. Schroder, J . Chem. Soc., Dalton Trans., 1759 (1990); A. Miiller, Comp. Coord. Chem., 2, 551 (1987).
3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates, and Other 1,l-Dithio Compounds (See 3.7.3, Table 1) 3.8.3.4.1 By Oxidation of the Metals and Their Complexes
Oxidation of low valent transition metal complexes with 1,l-dithio disulfides can yield 1,l-dithiolate derivatives’: 2C0(11)
+ 3(R,NC(S)S), +2Co(S2CNR2)3
(a)
Similarly, [M(S2CNR2)3]X,where M = Ni, Pd, and Pt and X = halogen, by oxidation of M(S2CNR& species with halogens or by oxidation of the M(SzCNR2)2X2complexes with (R2NCS2)2.Metal carbonyls are oxidized with (RzNCS2)’and dixanthogen. The eight-coordinated Mo [S2CN(C2H5)2]4forms by this procedure4. Oxidation of Fe(S2CNR2)2with N O produces3 Fe(S2CNR2)2N0, a squarepyramidal complex with nearly linear FeNO bonding5. Further oxidation5 with X2 (X = I, Br, SCN) or NOz gives six-coordinated products such as ONFe(S2CNR&X. Electrochemical oxidation of R u ( S ~ C N R ~yields )~ various cations6 such as RuZ[SzCN(Me)2]l. One of the more remarkable oxidations observed is formation of Ni [ S , C N ( ~ - B U ),C1 ~ ] from Ni [S2CN(n-Bu)J2 on reaction with excess ZnC1, in peroxide-free EtzO under anaerobic conditions’. This reaction is undoubtedly associated with the electron-pair acceptor acidity of Zn halides and the ease of forming oxidized species such as [R2NCS2CSNRzl2’ by loss of S. Etherates of BF3 oxidize Fe(S2CNRJ3 to Fe(S2CNR2)3BF4. A similar reaction with R u ( S ~ C N R ’ ) ~produces cation [RU~(S~CNR ) ~ ] [ C O ~ ( S ~ C N R ~ ) ~forms7 +.~Also, ] B F ~from reaction of BF3 with Co(SZCNRJ3. Thiuram monosulfide, [(R,NC(S)],S, is used as an oxidant forming’ Fe(SzCNR2)2C1from FeCI,. (J. P. FACKLER, K. G. FACKLER) 1. D. Coucouvanis, Prog. Inorg. Chem., 11, 233 (1970) 2. J. Willemse, J. A. Cras, J. J. Steggerda, C. P. Keijzers, Struct. Bond. (Berlin),28, 83 (1976); J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 3. J. P. Fackler, Jr., Prog. Inorg. Chern., 21, 23 (1976). 4. R. P. Burns, F. P. McCullough, C. A. McAuliffe, Adc. Inorg. Clzem. Radiochem., 26, 301 (1979). 5. D. Coucouvanis, Prog. Inorg. Chem., 26, 301 (1979). 6. A. R. Hendrickson, J. M. Hope, R. L. Martin, J . Chem. Soc., Dalton Trans., 2032 (1976). 7. L. H. Pignolet, B. M. Mattson, J . Chenz. Soc., Chem. Commun., 49 (1975).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
92 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond
3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals
3.8.3.4.2
By Ligand Replacement Reactions with Complexes of the Metals
Reaction of group IA, group IIA or [R4N]+ salts of the 1,l-dithio acids or phosphorodithioic (and related) acids with transition metal salts generally produces the metal dithioate13'. Crystalline lanthanide dithiocarbamates (except Pm) form3 from anhydrous MBr3 in anhydrous EtOH: MBr3
-
+ 3NaS2CN(CzH5),
+
M[S2CN(CzH5)2]3 3NaBr
(a)
The anion [M[S2CN(Et)& can be separated as the [Et4N]+ salt upon further addition of NaS2CN(Et)' and Et4NBr. Paramagnetic NMR shifts are observed with some spec i e ~Except ~. for Sc, Y, Tc, and Pm, 1,l-dithiolate complexes of all transition and inner transition metals are known5-*. Phosphorodithioates also are known for most of the transition and inner transition metals2. Various Ti and Zr complexes of stoichiometry M(S2CNR2),X4-, are known', where X = C1, Br, or R. In CHzC12, seven-coordinated Ti(S2CNR2)2Xspecies formg from TiX4 with NaS2CNR2. Ti(S2CNR2)2C12is isolated using reduced quantities of NaS2CNR2. Complexes of V(III), V(IV), and V(V) are known with 1,l-dithio ligands'. Both V(S2CNR2)3and V(S2CNR2)2Clform from VC13 and NaS2CNR2. The compounds Nb(SzCN2EtZ)nX5-n (X = Br, C1; n = 2-4) are obtained similarly7. With Ta(V), Ta(S2CNR& is obtained7. The dimeric [Nb2(S2CNEt2)5Brz]Bris obtained by similar procedures". Starting with alkylammonium or alkali metal salts of [SzCNRz]- in aqueous EtOH VOS04. 2 H 2 0 in H z O can be added to produce" VO(S2CNR2)2.Electron-pair donor bases add to produce six-coordinated species. With salts of dithiocarboxylates, eightcoordinated V(S,CR), complexes form5. Reaction" of (q5-C5H5)zVC12 with sodium xanthates or dithiocarbamates yields [(q5-C5H5)2VS2CY]+, Y = OR, NR2. Similar cyclopentadienyl products of Ti, Nb, and Mo form with phosphorodithioate ligands' from the halides. In MeOH, NbX5 and T a x 5 produce M(S2CNR2)2(0CH3)2X, X = C1, Br, NCS. These salts with [BF4]- anions are obtained in aqueous solutions: (q5-C5H5)zVC12 + NaS2COR + NaBF4
-
[(q5-C5H5)2VS2COR]BF4 + 2NaCl
(b)
The group VI dithiolates have been studied e ~ t e n s i v e l y ' ~ ' *The ~ ~ ~air-sensitive . Cr(S2CNR2)' complexes form from CrCl, and NaS2CNR2 in aqueous EtOH. The Cr(II),Mn(II), Fe(II), Cu(II), and Zn(I1) derivatives of M(S2CNEt2)2are isomorphous". Reaction of anhydrous CrCl, in a dry organic solvent with alkali metal salts of the dithio acids produces octahedral Cr(II1) species. The only examples' of 0-rich ligand complexes (Fig. 1) are obtained13 by reactions of K 2 C r 2 0 7with NaS2CNR2(R = Me, Et). Separation of products in HzO is accomplished by chromatography on silica using CHzClz. Xanthate and thioxanthate complexes are susceptible to ligand reactions with bases'. With xanthates, amines can produce dithiocarbamates or even dithiocarbonates ([S2C0l2-). The SR in thioxanthates also can be replaced by NR2 using nucleophilic amine~'~. Various oxomolybdenum and W species form by reaction of molybdenates or tungstates with alkali metal dithiolates. A satisfactory synthesis of M O ~ O , ( S ~ C N R ~ ) ~
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 93 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals
-N
Figure 1. The metal-ligand arrangement of Cr[S2CN(CZH5),][OSzCN(C2H5)z]. uses an Mo(V) salt in aqueous solutions and a greater than 4 : 1 excess of NaS2CNR2 at 0°C. Upon refluxing, M O ~ O ~ ( S ~ C isN obtained5. R ~ ) ~ In MeCN, MOCI4 reactsI5 with NaS2CNRz producing M o ( S ~ C N R ~ ) ~ . The quadruply bonded dimer M O ~ ( S ~ C O Cforms ~ H ~from ) ~ M ~ ~ ( a c e t a tand e)~ readily reacts with bases such as pyridine or THF, forming adducts. Thioxanthates of Mo(1V) form' from MoCI,(THF)~and (Bu4N)S2CSR.Various dithio acid salts react with [M0Cl6l3- producing Mo(S,CR),. Mixed ligand species, Mo(SZCNRz),Cl5-, (n = 1-4) are obtained from' MoC15 and NaSzCNRz in CHzC12.The air-stable thioxanthate complex MoO(S~CSC,H,)~is obtained by reactionI6 of PPh3 with M O ~ O ~ ( S ~ C S CPhosphines ~ H ~ ) ~ .also react with M O O ~ ( S ~ C N R ~ ) ~ :
+
M o O ~ ( S ~ C N R PPh3 ~)~
-
MoO(SZCNR2)z
+ OPPh3
(4
Various other oxomolybdenum dithiolate species are known's2, including M O Z ( S Z O ) ~ ( S ~ C NMo203(SPh)z(S2CNEtz)z, E~Z), M o z S ~ ( S Z C N R ZMoz03S(SzCRz)z, )~, and Mo2Sz[S2P(OEt)z]4. Tungsten complexes are relatively limited in number. Starting with WC14 and NaS2CNR2 in MeCN, W(SzCNR2)4is formed'. Organometallic species (q5-C5H5) W(C0)2S2CNRzform from5 (q5-C5H5)W(C0)3C1 and the NaSzCNRz. The dithiophosphate complex forms similarly2*6. Halide displacement reactions occur with sodium, 1,l-dithiolatesin solvents such as MeCN. Mananese(II), Mn(III), and Mn(1V) complexes are known with dithiolate ligands, and especially the dithiocarbamates. Starting with MnC1, in H z O under N z , the Mn(I1) species precipitate. With excess NaS,COEt, [Mn(S2COEt),] - is isolated" as the Et4Nf salt. With chelating bases present such as bipyridine, six-coordinated Mn(I1) complexes form which have MnS4Nz coordination. Oxidation by air in the presence of excess dithiolate generally produces Mn(II1) species. In CHZCIz or other organic solvents, M ~ I ( S ~ C N can R ~ )be~ oxidized by BF, to [Mn(S2CNR3),]BF3. The perchlorate salt also is known. Nuclear medicine has led to synthesis of several Tc dithiolates". Rhenium analogues generally are prepared first. Starting with ReC13(PPh3)z(NCCH3) in acetone, NaSzCNRz produces the Re(S2CNR2)3. With ReOC13(PPh3)z, Re203(S2CNR2)4 forms. The richness of Re chemistry is demonstrated by formation of ReN(S2CNEt&
94 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals
Figure 2. The bonding in ReN(S2CNEt2),. from ReNC12(PPh3)’ and NaS2CNEt2 in acetone”. This monomeric Re(V) complex contains distorted square-pyramidal ReS4N coordination (Fig. 2). Reviews of the synthesis of Fe(II), Fe(III), and Fe(1V) dithiocarbamates are available’,2.sx7.Xanthates, thioxanthates, dithiophosphates, and derivatives of dithio acids are known’,’. Reactions of iron halides with alkali metal dithiolates are commonly used for synthesis, e.g., in the procedure for preparing (q5-C4H4)Fe(C0)2(S2CNMe2):
+
-
(q5-C5H,)Fe(C0jZC1 NaSzCNMe2
acetone
+
(q5-C5H5)Fe(C0)2(S2CNMe2)NaCl
(4
The product contains a unidentate dithiolate ligand. The mercaptide-bridged dimer, [Fe(CO)2SMe(S2CNEt2)]2,is obtained by reacting [Fe(C0)3SMe]2 with NaS2CNEtz in 0,-free EtOH. The C ~ ~ - F ~ ( S ~ C N R complexes ~ ) ~ ( C Oare ) ~ prepared from Fe(I1) salts in H z O by reaction” with CO and NaSzCNR2. Whereas Ru(S,CNR,)~ complexes are obtained from K2RuC16 in aqueous NaS2CNR2,the presence of C O in EtOH solutions of RuC13 gives carbonyl derivatives such as R u ( S ~ C N R ~ ) ~ ( Cand O ) ~ [ R U ( S ~ C N R ~ ) ~ ( C O ) ~Dimers ] C ~ . such as [ R U ( S ~ C N R ~ ) ~ ]are B Robtained ~ from R U ( S ~ C N Rby ~ ) BF3 ~ oxidation”. Various R U ( S , C N M ~ ~complexes )~L~ (L = phosphines or phosphates) are prepared from Ru(I1) or Ru(II1) phosphine or phosphate complexes by reaction with NaS2CNMe2. Osmium(I1) and Os(II1) complexes with dithiocarbamate ligands are known’, the latter from (NH4)0sC16and NaS2CNR2.Acetates and trifluoroacetates of Os(I1) such as O S H ( O ’ C C H ~ ) ( P Preact ~ ~ ) ~with sodium salts of dithiocarbamates or xanthates in refluxing acetone” to produce O S ( S ~ C N R ~ ) , ( P Both P ~ ~ )xanthates ~. and dithiocarbamates form O S H C ~ ( C O ) ( P Pby~ ~halide ) ~ replacement. The susceptibility of 1,l-dithiolate complexes of Co(I1) to air oxidation varies substantially. Whereas aqueous solutions of Co(I1) with NaS’CNEt, are oxidized to C O ( S ~ C N E ~under , ) ~ oxygen-free conditions”, large R groups such as ~ i p e r i d i n e , ~ produce surprisingly air-stable Co(I1) products. While Co(I1) salts produce Co(S,P(OR),), products’ from aqueous alcoholic solutions of the dithiophosphonates, paramagnetic Co(S2PR2j2 products form with dithioph~sphinates’~ and with2’ [S2PFz]. The Co(I1) xanthate C O ( S ~ C O R )R~ = , iamyl, also is isolable26,although with R = Et, Co(S2CORj3is formed”, even under N,. Both electronic and steric factors control the ease of Co(I1) complex oxidation in solution to the Co(II1) species. The synthesis of Fe(II), Fe(III), Co(II), Co(III), and some group IIB complexes of [S,PX,] (X = F, CF3, C6H5,OC2H5,and CH3) starts with the alkali metal or ammonium dithiolate salt27. The C O S ~geometry is tetrahedral” in CCo(SJ’Me2)2ln.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 95 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.2 By Ligand Replacement Reactions with Complexes of the Metals
Alkylxanthate and thioxanthate complexes of Co(II1) form from alkali metal dithiolates and Co(I1) salts with air oxidation. The C O ( S ~ C S Rcomplexes, )~ as with Fe(S2CSR)3,Pd(S2CSR)2and Ni(S2CSR)2,eliminate CS2 to form mercaptide bridged dimers or oligomers’. Primary or secondary amines displace the OR or SR forming dithiocarbamates: M(S,CSR), NHR2 --* M(SZCNR2), + 2HSR (el
+
The arylxanthates of Co(I11) and other metal ions are obtained” from the thallium salts upon reaction with metal halides in EtOH: TIOAr
+ CS2
1 TIS2COAr + - MX,
benzene
TIS2COAr
1 TIX n n A few Co(II1) dithio acid derivatives, such as Co(S2CPh),, have been formed from reactions between organomagnesium halide reagents and CS2 and Co(I1) salts. A paramagnetic, S-rich dithioacid derivative of 2-aminocyclopentene, Co(S2CC5H6NH2) (S3CC5H6NH2)also exists2’. Both M(1) and M(II1) complexes of Rh and Ir are formed from metal halides and alkali metal salts of the sulfur ligands. Various phosphine derivatives4 such as Rh(S2CNR2)2(PPh3P) and Rh(S2CNMe2)(PPh3)2 form when phosphines are also present in the starting material [e.g., RhCI(PPh,),]. The dimer [Rh2(S2CNR2)5]BF3 forms’34from Rh(S2CNR2),with BF3. The nickel triad 1,l-dithiolates form from aqueous or ethanolic solutions of the bivalent metal ions’ and alkali metal salts of the ligand. Initial isolation of the alkali metal salt often is unnecessary. Mixing CS2 with an appropriate nucleophile (ROH, RSH, R2NH, etc.) under basic conditions in the presence of the transition metal ion produces the desired metal dithiolate. Symmetrization reactions3’ occur with nickel triad dithiolates to produce mixed ligand complexes: M(S2CNR2)Z
EtOH
+ ML2X2
- MS2COAr
-
+
2MLX(S2CNR2)
(g)
These mixed ligand species are useful starting materials for the synthesis organometallic l 2 react with the M(I1) derivatives such as PtPPh3(Me)(S2CNR2).Phosphines4% dithiolates to displace the sulfur ligands sequentially. Dithioacids, in the presence of basic sulfides and polysulfides, produce sulfur-rich nickel triad products, M(S2CR)2(S3CR). Starting with Zn(S3CR),, metathesis with metal halides produces’ M(S3CR),. Excess sulfur is removed from these sulfur-rich products with phosphines. The dimer, Pt2(S2CAr)4, forms when sulfur is removed from Pt (S3CAr)(S2CAr). Anionic dithiolates of the nickel triad elements form’,4 from dibasic 1,l-dithiols. In aqueous base, CS2 produces [Ni(S3CS),I2- and the sulfur-rich derivative [Ni(S,CS),]”-. The complex anions M(S2CX),I2- (X = S, 0, NR, CR2, where R is electron withdrawing) and their sulfur-rich analogues are isolated as crystalline salts upon the addition of large cations. Crystalline (Ph3P)2PtS2C0is formed25 in organic solvents by reacting Pt(S2COR)2with Ph3P. With excess [S2COR]-, [M(S2COR)J products can be obtained with the xanthates and some other 1,l-dithiolates. (J. P. FACKLER, K. G. FACKLER)
96
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.3 By Insertion of CS, (or P4S,,,) into Metal-Ligand Bonds
1. D. Coucouvanis, Prog. Inorg. Chem., 26,301 (1979); 11,233 (1970); G. D. Thorn, R. A. Ludwig, T h e Dithiocarbamates and Related Compounds, Elsevier, New York, 1962; S . R. Rao, Xanthates and Related Compounds, Dekke:, New York, 1971. 2. I. Haiduc, D. B. Sowerby, S.-F. Lu, Polyhedron, 14, 3389 (1995);S . E. Livingstone, Comp. Coord. Chem., 2, 633 (1987); J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 3. D. Brown, D. G. Holah, C. E. F. Rickard, J . Chem. Soc., Dalton Trans., 787 (1970). 4. H A. 0. Hill, D. Williams, N. Zars-Adarni, J . Chem. SOC.,Faraday Trans., 1494 (1976). 5. R. P. Burns, F. P. McCullough, C. A. McAuliffe, A d a Znorg. Chem. Radiochem., 23, 211 (1980). 6. F. J. Wasson, G. M. Woltermann, H. J. Stoklasa, Fortschr. Chem. Forsch., 35, 65 (1973). 7. J. Willemse, J. A. Cras, J. J. Steggerda, C. P. Keijzers, Struct. Bonding (Berlin),28, 83 (1976). 8. R. Eisenberg, Prog. Inorg. Chem., 12, 295 (1970). 9. A. N. Bhat, R. C. Fay, D. F. Lewis, A. F. Lindmark, S . H. Strauss, Inorg. Chem., 13,886 (1974). 10. D. J. Machin, J. F. Sullivan, J . Less-Common Met., 19, 413 (1969). 11. A. T. Casey, J. R. Thackery, Aust. J . Chem., 25, 2085 (1972); 27, 757 (1974); 28, 471 (1975). 12. J. P. Fackler, Jr., D. G. Holah, Znorg. Nuclear Chem. Lett., 2, 251 (1966). 13. J. M. Hope, R. L. Martin, D. Taylor, A. H. White, J . Chem. SOC.,Chem. Commun., 99 (1977). 14. J. P. Fackler, Jr., Am. Chem. SOC.,Adt.. Chem. Ser., 150, 394 (1976). 15. T. M. Brown, J. N. Smith, J . Chem. Soc., Dalton Trans., 1972, 1614. 16. J. A. Zubieta, G. B. Murphy, Can. J . Chem., 49, 2726 (1971). 17. D. G. Holah, C. N. Murphy, Can. J . Chem., 49, 2726 (1971). 18. J. Baldus, Adt.. Inorg. Chem., 41,2 (1994); K. Schwochau, Angew. Chem., Int. Ed. Engl., 33,2258 (1994). 19. J. F. Rowbottom, G . Wilkinson, J . Chem. SOC.,Dalton Trans., 826 (1972). 20. H. Buttner, R. D. Feltham, Inorg. Chem., 11, 971 (1972). 21. C. L. Raston, A. H. White, J . Chem. Soc., Dalton Trans., 2422 (1975). 22. P. B. Critchlow, S. D. Robinson, J . Chem. SOC.,Dalton Trans., 1367 (1975). 23. G. Marcogrigano, G. C. Pellacni, C. Preit, J . Znorg. Nuclear Chem., 36, 3709 (1974). 24. R. N. Mukherjee, V. V. Krishna Rao, J. Gupta, Indian J . Chem., 4, 209 (1966). 25. F. N. Tebbe, H. W. Roseky, W. C. Rode, E. L. Muetterties, J . Am. Chem. SOC.,90, 3578 (1968). 26. M. Delphine, L. Compin, Bull. SOC.Chim. Fr., 27, 469 (1920). 27. R. G. Cavell, E. D. Day, W. Byers, P. M. Watkins, Znorg. Chem., 11, 1759 (1972). 28. J. P. Fackler, Jr., D. P. Schussler, H. W. Chen, Synth. React. Inorg. Met. Org. Chem., 8,27 (1978); H. W. Chen, J. P. Fackler, Jr., Inorg. Chem., 17, 22 (1978). 29. P. Thomas, A. Poveda, 2.Chem., 11, 153 (1971). 30. H. W. Chen, J. P. Fackler, Jr., A. F. Masters, W. H. Pan, Inorg. Chim. Acta, 35, L333 (1979). 3.8.3.4.3 By Insertion of CS2 (or P&)
into Metal-Ligand Bonds
Transition metal amides, alkoxides, and mercaptides, hydrides, and related materials often react directly's2 with CS2 (or P4Sl0) to form metal dithiolates; e.g., Ta(NR2)sreacts with CS2 producing Ta(S,CNR,)s,3 or with Ti(IV), Zr(IV), and Hf(1V) complexes M(NR2)4,Ta(NR2)5,M o ~ ( O R )and ~, from which dithiocarbamate or xanthate products form. Dithiocarbamates and xanthates of several other transition metal ions are obtained by this method. With compounds containing M-R or M-H bonds, species such as M(CO),(RCS,) (M = Mn, Re; R = Me, Ph) and Re(S2CH)(C0)2(phosphine)2 can be obtained2.Various Ru(II), Os(II), and Ir(II1) derivatives of S2CH form by CS2 insertion4. Carbon disulfide also inserts into the Pt-F bond2. [PtF(PPh,),]HFz
+ CS2
-
[(Ph,P),Pt(S,CF)]HF,
The tricyclohexylphosphoniodithiocarboxylate [Mn2(C0)6(S2CPCy3)]has been synthesized by CS2 reaction with the PCy, and M ~ I ~ ( C OVarious ) ~ ~ ~ .CS2 insertion reactions with Ni complexes are described6. ( J . P. FACKLER, K. G. FACKLER)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
96
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.4 From Organic Thioacids, Thiophosphates, Xanthates 3.8.3.4.3 By Insertion of CS, (or P4S,,,) into Metal-Ligand Bonds
1. D. Coucouvanis, Prog. Inorg. Chem., 26,301 (1979); 11,233 (1970); G. D. Thorn, R. A. Ludwig, T h e Dithiocarbamates and Related Compounds, Elsevier, New York, 1962; S . R. Rao, Xanthates and Related Compounds, Dekke:, New York, 1971. 2. I. Haiduc, D. B. Sowerby, S.-F. Lu, Polyhedron, 14, 3389 (1995);S . E. Livingstone, Comp. Coord. Chem., 2, 633 (1987); J. A. Cras, J. Willemse, Comp. Coord. Chem., 2, 579 (1987). 3. D. Brown, D. G. Holah, C. E. F. Rickard, J . Chem. Soc., Dalton Trans., 787 (1970). 4. H A. 0. Hill, D. Williams, N. Zars-Adarni, J . Chem. SOC.,Faraday Trans., 1494 (1976). 5. R. P. Burns, F. P. McCullough, C. A. McAuliffe, A d a Znorg. Chem. Radiochem., 23, 211 (1980). 6. F. J. Wasson, G. M. Woltermann, H. J. Stoklasa, Fortschr. Chem. Forsch., 35, 65 (1973). 7. J. Willemse, J. A. Cras, J. J. Steggerda, C. P. Keijzers, Struct. Bonding (Berlin),28, 83 (1976). 8. R. Eisenberg, Prog. Inorg. Chem., 12, 295 (1970). 9. A. N. Bhat, R. C. Fay, D. F. Lewis, A. F. Lindmark, S . H. Strauss, Inorg. Chem., 13,886 (1974). 10. D. J. Machin, J. F. Sullivan, J . Less-Common Met., 19, 413 (1969). 11. A. T. Casey, J. R. Thackery, Aust. J . Chem., 25, 2085 (1972); 27, 757 (1974); 28, 471 (1975). 12. J. P. Fackler, Jr., D. G. Holah, Znorg. Nuclear Chem. Lett., 2, 251 (1966). 13. J. M. Hope, R. L. Martin, D. Taylor, A. H. White, J . Chem. SOC.,Chem. Commun., 99 (1977). 14. J. P. Fackler, Jr., Am. Chem. SOC.,Adt.. Chem. Ser., 150, 394 (1976). 15. T. M. Brown, J. N. Smith, J . Chem. Soc., Dalton Trans., 1972, 1614. 16. J. A. Zubieta, G. B. Murphy, Can. J . Chem., 49, 2726 (1971). 17. D. G. Holah, C. N. Murphy, Can. J . Chem., 49, 2726 (1971). 18. J. Baldus, Adt.. Inorg. Chem., 41,2 (1994); K. Schwochau, Angew. Chem., Int. Ed. Engl., 33,2258 (1994). 19. J. F. Rowbottom, G . Wilkinson, J . Chem. SOC.,Dalton Trans., 826 (1972). 20. H. Buttner, R. D. Feltham, Inorg. Chem., 11, 971 (1972). 21. C. L. Raston, A. H. White, J . Chem. Soc., Dalton Trans., 2422 (1975). 22. P. B. Critchlow, S. D. Robinson, J . Chem. SOC.,Dalton Trans., 1367 (1975). 23. G. Marcogrigano, G. C. Pellacni, C. Preit, J . Znorg. Nuclear Chem., 36, 3709 (1974). 24. R. N. Mukherjee, V. V. Krishna Rao, J. Gupta, Indian J . Chem., 4, 209 (1966). 25. F. N. Tebbe, H. W. Roseky, W. C. Rode, E. L. Muetterties, J . Am. Chem. SOC.,90, 3578 (1968). 26. M. Delphine, L. Compin, Bull. SOC.Chim. Fr., 27, 469 (1920). 27. R. G. Cavell, E. D. Day, W. Byers, P. M. Watkins, Znorg. Chem., 11, 1759 (1972). 28. J. P. Fackler, Jr., D. P. Schussler, H. W. Chen, Synth. React. Inorg. Met. Org. Chem., 8,27 (1978); H. W. Chen, J. P. Fackler, Jr., Inorg. Chem., 17, 22 (1978). 29. P. Thomas, A. Poveda, 2.Chem., 11, 153 (1971). 30. H. W. Chen, J. P. Fackler, Jr., A. F. Masters, W. H. Pan, Inorg. Chim. Acta, 35, L333 (1979). 3.8.3.4.3 By Insertion of CS2 (or P&)
into Metal-Ligand Bonds
Transition metal amides, alkoxides, and mercaptides, hydrides, and related materials often react directly's2 with CS2 (or P4Sl0) to form metal dithiolates; e.g., Ta(NR2)sreacts with CS2 producing Ta(S,CNR,)s,3 or with Ti(IV), Zr(IV), and Hf(1V) complexes M(NR2)4,Ta(NR2)5,M o ~ ( O R )and ~, from which dithiocarbamate or xanthate products form. Dithiocarbamates and xanthates of several other transition metal ions are obtained by this method. With compounds containing M-R or M-H bonds, species such as M(CO),(RCS,) (M = Mn, Re; R = Me, Ph) and Re(S2CH)(C0)2(phosphine)2 can be obtained2.Various Ru(II), Os(II), and Ir(II1) derivatives of S2CH form by CS2 insertion4. Carbon disulfide also inserts into the Pt-F bond2. [PtF(PPh,),]HFz
+ CS2
-
[(Ph,P),Pt(S,CF)]HF,
The tricyclohexylphosphoniodithiocarboxylate [Mn2(C0)6(S2CPCy3)]has been synthesized by CS2 reaction with the PCy, and M ~ I ~ ( C OVarious ) ~ ~ ~ .CS2 insertion reactions with Ni complexes are described6. ( J . P. FACKLER, K. G. FACKLER)
3.8.3Formation of the Sulfur-Transition and Inner-Transition Metal Bond 97 3.8.3.5Bidentate (excluding 1,l -dithiols) and Polydentate Sulfur Donor 3.8.3.5.1By Sulfur Addition, Oxidation, and Sulfur Abstraction Reactions D. Coucouvanis, Prog. Inorg. Chem., 26, 300 (1979). R. P. Evans, F. P. McCullough, C. A. McAuliffe, Adc. Inorg. Chem., 23, 211 (1980). D. C. Bradley, M. Gitlitz, J . Chem. SOC., A , 1152 (1979). S. D. Robinson, A. Sahajpal, Inorg. Chem., 16, 2718 (1977). D. Miguel, V. Riera, J. A. Miguel, X. Solans, M. Font-Altaba,J. Chem. SOC.,Chem. Commun.,472 (1987). 6. L. Sacconi, F. Mani, A. Bencini, Comp.Coord. Chem., 5, l(1987).
1. 2. 3. 4. 5.
3.8.3.5 From Bidentate (excluding 1,l-dithiols) and Polydentate Sulfur Donor Ligands 3.8.3.5.1 By Sulfur Addition, Oxidation, and Sulfur Abstraction Reactions
Heating NiS and PhCzPh together in toluene yields's2 the diamagnetic Ni(S2C2Ph2)2.Transition metal complexes [NBu,J2 M(SzC2(CN)2)z(M = Co, Ni, Pd, Pt) form by S extrusion and dimerization of [S2CN12-. Metal complexes of 1,2dithiolates with nearly all of the transition elements are known3-'. Work with Ni has been prolific6. An important synthetic route to the 1,2-dithiolenes is the acyloin or benzoin reaction': 2RC(O)CH(OH)R
-
+ P4Sl0
+
[R2C2S2P(S)S-I2 H2S
M"+, H ~ O
M(S2C2R2ln (a)
Another particularly successful route for synthesis of 1,Zdithiolenes is the oxidation of low valent metal phosphines or carbonyls with dithiete:
s-s
+
M(C0)rj
M[SZC*(CF3)2]3 + 6CO
(CF3*CF)
(b)
(M = Mo, W)
Owing to electronic delocalization in the ligands, cationic and anionic metal complexes are formed by oxidation or reduction of the neutral complexes'. Metal complexes of 1,3-monothio and dithioketones can be obtainedg by reduction of 1,2-dithiolium cations in the presence of [HSI-, [HOI-, and transition metal ions. Reaction of H2S at 0°C in EtOH HC1 with the metal P-diketonates, M(acac),, produces the monothio, M(Sacac), , and dithio-P-diketone, M(SacSac), derivatives (N = Mi, Pd, Pt, Co): M(acac),
+ HzS O
HC1 ~
M(SacSac), H
+ nHzO
The Fe(SacSac), and Ni(SacSac), and analogues are prepared from metal salts and the 1,2-dithiolium cations by NaBH, reduction. A symmetrization reaction of Ni(PEt3)2C12with Ni(SacSac), in organic solvents produces the mixed ligand species" NiC1(SacSac)PEt3. (J. P. FACKLER, K. G. FACKLER)
1. G. N. Schrauzer, V. Mayweg, J . Am. Chem. SOC.,84, 3221 (1962). 2. S. E. Livingstone, Q. Reu. Chem. SOC., 19, 386 (1965).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.3Formation of the Sulfur-Transition and Inner-Transition Metal Bond 97 3.8.3.5Bidentate (excluding 1,l -dithiols) and Polydentate Sulfur Donor 3.8.3.5.1By Sulfur Addition, Oxidation, and Sulfur Abstraction Reactions D. Coucouvanis, Prog. Inorg. Chem., 26, 300 (1979). R. P. Evans, F. P. McCullough, C. A. McAuliffe, Adc. Inorg. Chem., 23, 211 (1980). D. C. Bradley, M. Gitlitz, J . Chem. SOC., A , 1152 (1979). S. D. Robinson, A. Sahajpal, Inorg. Chem., 16, 2718 (1977). D. Miguel, V. Riera, J. A. Miguel, X. Solans, M. Font-Altaba,J. Chem. SOC.,Chem. Commun.,472 (1987). 6. L. Sacconi, F. Mani, A. Bencini, Comp.Coord. Chem., 5, l(1987).
1. 2. 3. 4. 5.
3.8.3.5 From Bidentate (excluding 1,l-dithiols) and Polydentate Sulfur Donor Ligands 3.8.3.5.1 By Sulfur Addition, Oxidation, and Sulfur Abstraction Reactions
Heating NiS and PhCzPh together in toluene yields's2 the diamagnetic Ni(S2C2Ph2)2.Transition metal complexes [NBu,J2 M(SzC2(CN)2)z(M = Co, Ni, Pd, Pt) form by S extrusion and dimerization of [S2CN12-. Metal complexes of 1,2dithiolates with nearly all of the transition elements are known3-'. Work with Ni has been prolific6. An important synthetic route to the 1,2-dithiolenes is the acyloin or benzoin reaction': 2RC(O)CH(OH)R
-
+ P4Sl0
+
[R2C2S2P(S)S-I2 H2S
M"+, H ~ O
M(S2C2R2ln (a)
Another particularly successful route for synthesis of 1,Zdithiolenes is the oxidation of low valent metal phosphines or carbonyls with dithiete:
s-s
+
M(C0)rj
M[SZC*(CF3)2]3 + 6CO
(CF3*CF)
(b)
(M = Mo, W)
Owing to electronic delocalization in the ligands, cationic and anionic metal complexes are formed by oxidation or reduction of the neutral complexes'. Metal complexes of 1,3-monothio and dithioketones can be obtainedg by reduction of 1,2-dithiolium cations in the presence of [HSI-, [HOI-, and transition metal ions. Reaction of H2S at 0°C in EtOH HC1 with the metal P-diketonates, M(acac),, produces the monothio, M(Sacac), , and dithio-P-diketone, M(SacSac), derivatives (N = Mi, Pd, Pt, Co): M(acac),
+ HzS O
HC1 ~
M(SacSac), H
+ nHzO
The Fe(SacSac), and Ni(SacSac), and analogues are prepared from metal salts and the 1,2-dithiolium cations by NaBH, reduction. A symmetrization reaction of Ni(PEt3)2C12with Ni(SacSac), in organic solvents produces the mixed ligand species" NiC1(SacSac)PEt3. (J. P. FACKLER, K. G. FACKLER)
1. G. N. Schrauzer, V. Mayweg, J . Am. Chem. SOC.,84, 3221 (1962). 2. S. E. Livingstone, Q. Reu. Chem. SOC., 19, 386 (1965).
98
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2-, [HS-I)
J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). G. N. Schrauzer, Trans. Met. Chem., 4 , 299 (1968). U. T. Mueller-Westerhoff,B. Vance, Comp. Coord. Chem., 2, 595 (1987). L. Sacconi, F. Mani, A. Bencini, Comp. Coord. Chem., 5, l(1987). R. P. Burns, C. A. McAuliffe, Adt’. Inorg. Chem. Radiochem, 22, 303 (1979). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, Wiley-Interscience,5th ed., New York, 1988, p 539. 9. T. N. Lockyer, R. L. Martin, Prog. Inorg. Chem., 27, 223 (1980). 10. J. P. Fackler, Jr., A. F. Masters, Inorg. Chim. Acta., 27, 223 (1980). 3. 4. 5. 6. 7. 8.
3.8.3.5.2 By Ligand Substitution Reactions
Anionic 1,2-dithiolates commonly form by ligand substitution reactions’,’. Sodium salts of aromatic 1,2-dithiols such as toluene-l,2-dithiol are representative of this chemistry:
MX,
+
n
rSd) - \.=:b n-
Na
(a)
nNaX t nNat
Similar results are obtained starting with Na2SzCz(CN),. Tables listing most transition metal 1,2-dithiolates are available3. Sulfur-containing amino acid complexes4 of the transition metals and numerous other chelating thiol ligand5 have been prepared and studied. These materials often form from ligand alkali metal salts upon reaction with transition metal halides. A review of this chemistry is available6. (J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4. 5. 6.
J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). R. P. Burns, C. A. McAuliffe, Adr. Inorg. Chem. Radiochem., 22, 303 (1979) U. T. Mueller-Westerhoff,B. Vance, Comp. Coord. Chem., 2, 595 (1987). C. A. McAuliffe, S. G. Murray, Inorg. Chim. Acta Rec., 6, 103 (1972). S. E. Livingstone, Q.Rev. Chem. Soc., 19, 386 (1965). C. G. Kuehn, S. S . Isied, Prog. Inorg. Chem., 27, 153 (1980).
3.8.3.6 From Sulfur Anions (S2-, HS-, S:-, Inner Transition Metal Bonds
RS-)-Transition and
3.8.3.6.1 With Sulfur Anions (Sz-, [HS-1)
This section contains four subsections covering the following topics: (i) the use of NaSH and related salts in hydroxylic solvents, (ii) the use of metal sulfides as ligands, (iii) the use of main group sulfides as reagents and ligands, and (iv) the synthesis of M S H complexes. ( i ) Formation of M-S Bonds Using Classical S“, SH- Sources. Many transition metal sulfides form by direct reaction of metal cations with aqueous solutions of Na2S or other ionic “sulfide” salts. Hydrated sodium sulfide is better described as
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
98
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2-, [HS-I)
J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). G. N. Schrauzer, Trans. Met. Chem., 4 , 299 (1968). U. T. Mueller-Westerhoff,B. Vance, Comp. Coord. Chem., 2, 595 (1987). L. Sacconi, F. Mani, A. Bencini, Comp. Coord. Chem., 5, l(1987). R. P. Burns, C. A. McAuliffe, Adt’. Inorg. Chem. Radiochem, 22, 303 (1979). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, Wiley-Interscience,5th ed., New York, 1988, p 539. 9. T. N. Lockyer, R. L. Martin, Prog. Inorg. Chem., 27, 223 (1980). 10. J. P. Fackler, Jr., A. F. Masters, Inorg. Chim. Acta., 27, 223 (1980). 3. 4. 5. 6. 7. 8.
3.8.3.5.2 By Ligand Substitution Reactions
Anionic 1,2-dithiolates commonly form by ligand substitution reactions’,’. Sodium salts of aromatic 1,2-dithiols such as toluene-l,2-dithiol are representative of this chemistry:
MX,
+
n
rSd) - \.=:b n-
Na
(a)
nNaX t nNat
Similar results are obtained starting with Na2SzCz(CN),. Tables listing most transition metal 1,2-dithiolates are available3. Sulfur-containing amino acid complexes4 of the transition metals and numerous other chelating thiol ligand5 have been prepared and studied. These materials often form from ligand alkali metal salts upon reaction with transition metal halides. A review of this chemistry is available6. (J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4. 5. 6.
J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). R. P. Burns, C. A. McAuliffe, Adr. Inorg. Chem. Radiochem., 22, 303 (1979) U. T. Mueller-Westerhoff,B. Vance, Comp. Coord. Chem., 2, 595 (1987). C. A. McAuliffe, S. G. Murray, Inorg. Chim. Acta Rec., 6, 103 (1972). S. E. Livingstone, Q.Rev. Chem. Soc., 19, 386 (1965). C. G. Kuehn, S. S . Isied, Prog. Inorg. Chem., 27, 153 (1980).
3.8.3.6 From Sulfur Anions (S2-, HS-, S:-, Inner Transition Metal Bonds
RS-)-Transition and
3.8.3.6.1 With Sulfur Anions (Sz-, [HS-1)
This section contains four subsections covering the following topics: (i) the use of NaSH and related salts in hydroxylic solvents, (ii) the use of metal sulfides as ligands, (iii) the use of main group sulfides as reagents and ligands, and (iv) the synthesis of M S H complexes. ( i ) Formation of M-S Bonds Using Classical S“, SH- Sources. Many transition metal sulfides form by direct reaction of metal cations with aqueous solutions of Na2S or other ionic “sulfide” salts. Hydrated sodium sulfide is better described as
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
98
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2-, [HS-I)
J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). G. N. Schrauzer, Trans. Met. Chem., 4 , 299 (1968). U. T. Mueller-Westerhoff,B. Vance, Comp. Coord. Chem., 2, 595 (1987). L. Sacconi, F. Mani, A. Bencini, Comp. Coord. Chem., 5, l(1987). R. P. Burns, C. A. McAuliffe, Adt’. Inorg. Chem. Radiochem, 22, 303 (1979). F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, Wiley-Interscience,5th ed., New York, 1988, p 539. 9. T. N. Lockyer, R. L. Martin, Prog. Inorg. Chem., 27, 223 (1980). 10. J. P. Fackler, Jr., A. F. Masters, Inorg. Chim. Acta., 27, 223 (1980). 3. 4. 5. 6. 7. 8.
3.8.3.5.2 By Ligand Substitution Reactions
Anionic 1,2-dithiolates commonly form by ligand substitution reactions’,’. Sodium salts of aromatic 1,2-dithiols such as toluene-l,2-dithiol are representative of this chemistry:
MX,
+
n
rSd) - \.=:b n-
Na
(a)
nNaX t nNat
Similar results are obtained starting with Na2SzCz(CN),. Tables listing most transition metal 1,2-dithiolates are available3. Sulfur-containing amino acid complexes4 of the transition metals and numerous other chelating thiol ligand5 have been prepared and studied. These materials often form from ligand alkali metal salts upon reaction with transition metal halides. A review of this chemistry is available6. (J. P. FACKLER, K. G. FACKLER)
1. 2. 3. 4. 5. 6.
J. A. McCleverty, Prog. Inorg. Chem., 10, 49 (1968). R. P. Burns, C. A. McAuliffe, Adr. Inorg. Chem. Radiochem., 22, 303 (1979) U. T. Mueller-Westerhoff,B. Vance, Comp. Coord. Chem., 2, 595 (1987). C. A. McAuliffe, S. G. Murray, Inorg. Chim. Acta Rec., 6, 103 (1972). S. E. Livingstone, Q.Rev. Chem. Soc., 19, 386 (1965). C. G. Kuehn, S. S . Isied, Prog. Inorg. Chem., 27, 153 (1980).
3.8.3.6 From Sulfur Anions (S2-, HS-, S:-, Inner Transition Metal Bonds
RS-)-Transition and
3.8.3.6.1 With Sulfur Anions (Sz-, [HS-1)
This section contains four subsections covering the following topics: (i) the use of NaSH and related salts in hydroxylic solvents, (ii) the use of metal sulfides as ligands, (iii) the use of main group sulfides as reagents and ligands, and (iv) the synthesis of M S H complexes. ( i ) Formation of M-S Bonds Using Classical S“, SH- Sources. Many transition metal sulfides form by direct reaction of metal cations with aqueous solutions of Na2S or other ionic “sulfide” salts. Hydrated sodium sulfide is better described as
3.8.3 Formation of the Sulfur-Transition and inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S* - , [ HS -1)
99
-
NaSH'NaOH, since the second pK, of SH- is 19, much greater than 14 for H 2 0 . Thus, S2- does not exist in appreciable amounts in H z O (and probably not in alcohols). Conversion of metal cations to metal sulfides using the mixture of NaSH and NaOH is efficient because of the greater nucleophilicity of SH-. The intermediate MSH species, as monomers or as M,(p-SH)-containing oligomers, are readily deprotonated by O H - , yielding binary metal sulfides:
+
M(H20)gC SH-
-
-H20
-
M(H20)5SHC
OH-
- 5H,O
MS
(a)
Many simple aquo-metal complexes react with H2S or SH- to give insoluble binary metal sulfides. This method has been described preparation of NiS, a-CoS, and both green and red forms of MnS'. Reaction of DMF-metal salt solutions with H2S yields so-called organosols, colloidal forms of metal sulfides. This approach has been used for several first transition series divalent metal ions'. Most other binary metal sulfides are best prepared from the elements or by decomposition of thiometallate salts. The hydrolytic sensitivity of early transition metal compounds demands that their syntheses be conducted with anhydrous reagents. NazS and Li2S, usually generated by reaction of the elements in anhydrous NH33,have been used in synthesis of Ti&, ZrS2, HfS2, VS2, and MoS2. Reaction of LizS with NbC15 and TaCl, produces the reduced species NbSz and TaS,, respectively: 2MClS + 5Li2S-
2MS2
+ lOLiCl + S
(b)
Separation of alkali metal halides from the moisture-sensitive products can be problematic4. The solid state reaction of finely divided Na2S with MoC15 produces MoSZ5. Use of LizS in the synthesis of organometallic sulfides is illustrated by its reaction with (CsMes)TaC14,giving both (CsMe5)TaS:- and (C5Me5)3Ta3Sa-;the latter indicates the reducing nature of LizS [see reaction (b)]. Synthesis of (C5Mes)TaS:- is optimally conducted with Liz&, which is less reducing than Li2S. The binding of the small alkali metal cation to the anionic sulfide centers may confer stabilization not available for the corresponding quaternary ammonium salts. The Li+ derivatives of MS2- (M = V, Nb, Ta) are handled similarly6. The elements V, Nb. Ta, Mo, W, and Re form soluble anionic tetrasulfides'. Usually these syntheses are accomplished using a solution of H2S in aqueous NH3, i.e., NH:SH-. This approach applies to Vv, Mo", W"', and Rev", giving the corresponding MS2- (M = V, n = 3; M = Mo, W, n = 2; M = Re, n = 1)'. The related Nb and Ta compounds cannot be prepared using aqueous reagents (see below). Whereas aqueous solutions of (NH4)3VS4are unstable, the Li' salt of VSi- gives stable solutions in organic solvents. This salt can be prepared by treatment of (NH4)3VS4with Liz& liberating NH3'. The NH; salts of Mo, W, and Re thiometallates undergo smooth cation exchange to the corresponding NR; and PPh: salts. These salts exhibit good solubility in polar organic solvents; e.g., MeCN and D M F are widely used in synthesis. The very useful red and yellow thioanions MoSi- and WSi-, respectively, form from the corresponding Mo70gq and WOi- salts. Intermediates in thiation of the oxides, species like MoS,O$- and M0S302-, are isolated in good yields by conducting the reaction for shorter times":
+ SH-M 0 3 S 2 - + SH-MOi-
M03S2- + OHMO$-
+ OH-
(4 (4
100 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2 - , [HS -1)
Whereas NH2SH- can be used for synthesis of ReS4, it is more efficient to react aqueous polysulfide with R e 0 4 in the presence of Et4NCl. Conversion of the cluster Mo6C1:, to MO&& (L = neutral amine ligand) is accomplished using a combination of NaSH and NaOC4H9 in donor solvents such as pyridine. Reactions are slow, indicating the relative inertness of the face-capping chloride ligands. Terminal ligands in Mo,S,(py), are amenable to ligand exchange. An alternative “building block approach” begins with the solid state cluster compound Mo3S7C14, which is depolymerized with PEt,; the resulting M o cluster ~ is subsesquently reductively coupled using Mg. The Cr6S8L6clusters cannot be prepared analogously. Instead, CrCl, is treated with NaHS, in the presence of the PEt,. Na,S, itself is not useful in this synthesis”. In contrast, an attempt to prepare an Mn sulfido cluster by reaction of Mn”’(02CCH3)3. 2 H z 0 , Me3TACN (TACN = 1,4,7-triazacyclononane)and “(NH&S” resulted in the tetrasulfido complex Mn”(S4)(H20)(Me3TACN)12. Metal sulfides can be prepared at elevated temperatures from alkali metal sulfides, generated in situ by reaction of alkali metal carbonates and sulfur; e.g., a melt of N a 2 C 0 3 and KzCO3, S8, and Fe generates KFeSz: 4KzCO3
+ 13s + 6Fe-
6KFeS2
+ KZSO4 + 4 c 0 2
( g)
The same product is obtained when K2S, is generated from K2S and S813.The related, but molecular, binary iron sulfido anion FelsS:E- is formed from LizS and Fe amidato complexes. These are isolated with mixed cations, both quaternary ammonium cations and Na’, the latter indicating the high basicity of the p z - S atoms at the interior of the toroid-shaped anionI4. Iron sulfides have been heavily studied, leading to some stoichiometrically simple compounds. Illustrative is the reaction of NazS with FeBr, in DMF, which is claimed to give Fe4S4Br;-”. The cubane cluster Fe,S4Cl:-, prepared from Fe4S4(SR)i- by reaction with acyl chloride, reacts with Li2S, yielding the double cluster [Fe4S4Cl3I2S4-’,:
The extensive chemistry of the Fe-S-SR clusters is discussed elsewhere in this series. Treatment of Fe(CO)5with “Na2S” in the presence of NaOEt under CO pressure gives Fe3(p,-S)(CO),H-, which protonates to the neutral dihydride”. Iron nitrosyl sulfides, the first synthetic metal sulfido clusters, include Roussin’s “red salt”, a hydrated alkali metal salt of [FezSz(N0)4]2-, and the corresponding “black salt”, NHf [Fe,S,(NO),] -. These can be interconverted by acid-base reactions:
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 101 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2- , [ HS -1)
s
I
7T
\/
0)
The black salt forms by complicated but easily executed reactions of F e z + ,NO;, and NH;SH-l8. The anion in the “red salt”, [Fe,Sz(NO)4]Z-, is isolated as its Ph,As+ salt by treatment of FeZIz(N0), with LiZSl9. Addition of HzS to Fe2+,Co2+,and Ni2+ solutions in the presence of PEt3 yields the clusters [Fe,&(PEt3)6]2 +, [COgS8(PEt3)6] +, and Ni9S9(PEt3)%+, respectively. These reactions almost certainly proceed via attack of SH- at the metal-PEt3 complexz0. Treatment of the adamantoid cluster Co,(SPh):i with NaSH gives the c O & ( s P h ) ~ - ’I. Sulfides of the heavier metals in groups IB, IIB, and VIII behave and are synthesized quite differently from their lighter counterparts. Solutions of NaSH and [(arene)RuClzlz react to give the electroactive clusters ( a r e ~ ~ e ) ~ R u”.~ S ;Related + reactions with [(C5MeS)MC12], give clusters that are trigonal prismatic [(C5Mes)Ml3S~’and cuboidal [(C5Me5)MI4S4, depending on the M/SH- ratio (M = Rh, Ir)23. cisPtClz(PMezPh), reacts with S z - yielding dimer Pt2S2(PR3), or the open clusters [Pt3(p3-s)z(PR3)6]2 +,depending on the reaction stoichiometry. (ii) Formation of M-S Bonds Using Transition Metal Sulfides as Ligands. Metal-sulfur linkages can be made through use of soluble metal sulfides as ligands. Tetrathiometallates MSI- (M = V, Mo, W, Re) are widely used for these purposes. Generally the tetrathiometallate ligand is structurally-but not electronically-related to bidentate dithiocarboxylate ligands (RCS; ). Inorganic examples include Ni(MoS4):-, Fe(MoS,):-, Rh(WS4):-, and VS4[FeC12]:- 24. Several related organometallic compounds exist, e.g., MOS4 [CpzNb12,WS4[Rh(diene)12,MOS4 [CpRu(PPh,)], , and WS4[Pd(ally1)]225. Many cubane clusters form by reactions of MSI- and metal halides. This methodology permits incorporation of the thiometallate into the cluster. Such a multicomponent reaction involves combination of VS:- and FeCl, in DMF, yielding the cubane cluster [FeCI],[V(DMF),]Si. An intermediate is the previously mentioned VS4[FeC12]i- z 6 . One 0x0 in “ M 0 ~ 0 ~ ( a’”,q )obtained ~ by reduction of MOO:-, can be sulfided with SH- giving the corresponding versatile starting reagent “ M 0 ~ 0 , S ( a q’””. ) ~ Reduction of “ M 0 ~ 0 , S ( a q ) ~ ’ ”with BH, generates a mixture, which is separated by cation exchange chromatography to give Mo4S4(H20):i, Mo3S4(H2O);’ 2 8 , and other compounds. The trinuclear species Mo3S4(H20);’ binds other metals as a tridentate S3 ligand; e.g., treatment of M o , S ~ ( H ~ O ) with ~C~~ Pd black gives cuboidal [ M o ~ S ~ ( H ~ O ) ~ P in ~C which I ] Cthe ~ ~H 2 0 ligands can latter be displaced by amines and the chloro ligand by n-acid l i g a n d ~ Related ~~. Mo-S-0 compounds are accessed by oxidative removal of sulfido ligands from M o ~ O ~ ( ~ ( - S ) ~ ( -S ~(see ) ( Salso ~ ) ’3.8.3.6.2). Treatment of this anion with a D M F solution of Iz results in loss of the S i - ligand, giving M O ~ O ~ ( ~ - S ) , ( S , ) ( D MThe F)D ~ ~M~F. ligands are labile and can be replaced by anionic ligands such as dithiolates and CSH; 31. Complexes with p 2 - S ligands usually can be employed as ligands, especially when such complexes are anionic or lacking strong n-acceptor coligands. The dianions
102 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S' - , [ HS -1)
-
[Fe2S2(N0),l2- and Fe2S2(CO)i- react with metal halides [e.g., PtC12(PR3)2]to give (6)32: trimetallic cluster compounds such as (PPh3)2Pt(p3-S)2Fe2(Co)6 Fe2S2(CO)i-
+ PtC12(PPh3)2
+
(C0)6Fe2(p3-S)2Pt(PPh3)22c1-
(j)
The carbonyl Fe2S2(CO)g- is prepared by chemical reduction of the neutral tetrahedrane FezS2(CO),. Neutral complexes containing the M2(p2-S)fragment also serve as metalloligands, as illustrated by complexes formed from Pt2S2(PPh3)433. Trigonal prismatic Fe6S6Cli-, which has six triply bridging sulfido centers, forms adducts with metal carbonyls of the type Fe,S&l,j[M(CO)3]~- (n = 3,4; M = MO, w)34. (iii) Synthesis of M-S Bonds Using Main Group Sulfides as Reagents and Ligands. An important sulfide transfer reagent is (Me3Si)2S,which serves as a source of s2-:
MC14 + 2(Me3Si),S-
MS2 + 4Me3SiC1
(k)
Conveniences associated with (Me3Si)2Smethodology are as follows: (1) (Me3Si)2Sis soluble in many organic solvents (it is quite sensitive to moisture, however); ( 2 ) the by-products, such as Me3SiC1and (Me3Si)20,are easily removed by either evaporation or extraction into hydrocarbon solvents; and (3) the reactions of (Me3Si)2Swith metal halides and oxides typically occur at mild temperatures. The malodorous reagent (Me,Si),S (b.p. 162°C)is prepared on large scale by reaction of Na,S (prepared from Na and S in anhydrous NH3 or in THF) with Me3SiC135.This reagent has been used to prepare sulfides of Ti, V, Cr, Mo, W, and Fe, usually from the corresponding chlorides36. Treatment of WF6 and MoF, with (Me,Si),S gives the corresponding trisulfides, which probably should be described as M4+(S2-)(S:-). These exothermic reactions occur in CH2C12solution, and the products precipitate. The phases formed in these reactions are determined by the precursor halide. [Contrast the reactions of NbC15 with Lips and (Me3Si)2S,which give NbS2 and Nb2S5,respectively.] Further study is needed to fully assess the phase and compositional purity of the solid state materials produced by this method. Reactions of binary metal halides and (Me3Si)2Sprobably proceed via mixed sulfido-halo compounds, indicated by isolation of polymeric TiSC12 from 1:1 reaction of (Me3Si)2Sand TiCl,. In the presence of Et,NCl, TiSC12 dissolves giving square-pyramidal (NEt4)2TiSC1437. (Me3Si)2Sis widely used in the synthesis of molecular sulfido complexes. For late transition metals, strongly bound coligands such as phosphines or cyclopentadienyl inhibit polymerization to the binary metal sulfide. Representative transformations involve conversion of MC12(PR3)2(M = Ni, Co) to [NiC1]2[Ni(PPh3)]6(p-s), and [Co(P(r-Bu),)],(p-S),, respectively3'. Treatment of (MeC5H4)TiC12(THF), with (Me,Si),S yields [(MeC5H4)TiI4S439. In principle (Me3Si)2Scan replace oxide and alkoxide ligands, the coproducts being (Me3Si)20 and Me,SiOR, respectively, as in conversion of W5Ta0:; into W5TaSO:; 40. Sometimes these reactions are accompanied by reduction: e.g.,V(O)(salen) and Mo,O:; are reduced by (Me3Si)2S,to V(OSiMe3)(salen)and M o 3 0 S i - , respectively4'. Treatment of M(OEt), (M = Nb, Ta) wih (Me3Si)2Sin the presence of Et4NC1 gives (NEt4)5M6S17r a rare example of a condensed binary metal sulfide in which all metals are do 42. Tetrathiometallates of Nb and Ta are prepared using a variation of the (Me3S&S method in which this reagent is pretreated with alkoxide to give Me3SiS-. Treatment of this reagent with pentaalkoxides M(OEt)5gives the corresponding Li3MS4,
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 103 3.8.3.6 Sulfur Anions-Transitionand Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2- , [ HS -1)
-
isolated as MeCN and TMEDA s ~ l v a t e s ~ ~ : (Me3Si)2S+ LiOEt 4Me3SiSLi + Nb(OEt),
Me3SiSLi + EtOSiMe,
(1)
Li3NbS4 + 4EtOSiMe3 + LiOEt
(4
The Si-S bonds in complexes like Fe(OEP)SSiMe, react with metal halides, affording sulfido-bridged heterometallic compounds44. Other main group sulfides, used less often as sulfide sources, include the nonmolecular compounds B2S3, Sb2S3,SnS2, and PbS. Treatment of V(0) (salen) with B2S3 gives V(S)(salen), in contrast to reduction of this oxide by (Me3Si)2S4s.High-temperature (550°C)reaction of Re3Br9with PbS in the presence of KBr gives the anion Re&$ri-, crystallized as its PPh: salt46.Treatment of NbCIS with Sb2S3gives NbSC1347. Anionic main group sulfido species are widely used as ligands via formation of M-S bonds: e.g., anions Me2SiS:-, PhPSi-, and ASS:- combine with metal halides to give M-S-M' linkage. Illustrative are the Cp2Ti derivatives shown in Scheme 14*.
Scheme 1 Reaction of Mn2+ with (NMe4)2MnGe4Slo49.
the
NMe:
salt
of
Ge4S:,
gives the polymer
(iv) Synthesis of M-SH Compoundsfrom NaSH and Its Equivalent. Alkali metal salts of SH- are used in synthesis of complexes containing SH ligands. C ~ R U ( P P ~ ~ ) ~ S H and Ni(SH)2(PhZPCH2CH2PPh2) form in this way from the corresponding chlorides. The bis(tripheny1phosphine)iminium salt of [SH] converts [W(CO),I] - to [W(CO),SH] -, which has an extensive S-centered chemistry5'. The corresponding neutral Mn carbonyls behave similarly. The labile solvate ligand in M O ( C O )(THF) ~ is easily displaced by SH- ion, giving the dimers [Mo,(SH),(CO),]. Halide metathesis using MSH (M =Na, Li) or Et3NH+SH- leads often to metal complexes containing the sulfhydryl ligand, e.g., (C,H,),M(SH), (M = Ti, Mo, W),'. Cluster-bearing SH ligands are prepared by reaction of cluster halides with SH-, as well as by condensation of mononuclear SH compounds, e g , Mn(CO),SH to Mn4(CO)12(SH)4. Sometimes NaSH serves as a source of the radical S- (i.e.,half of S$-) concomitant with evolution of hydrogen. Illustrative is reaction of (C5Me5)4R~4C14 with NaSH yielding cuboidal (C5Me&Ru4S4. A related but stepwise reaction involves conversion of (MeC5H4)Ru(PPh3)ZSH to (MeCSH4)4R~4S4s2:
-
4(C5H4Me)Ru(PPh3)2SH
+
(C5H4Me)4R~4S42H2
+ 8PPh3
(4
Analogous to using (Me3Si)2Sas a surrogate for S 2 - , Me3SiS- serves as a source of SH-. Thus Ru(N)Me3Br- and Me3SiSNa react to give Ru(N)Me3(SSiMe3)-,which hydrolyzes to the SH complexs3. (T. B. RAUCHFUSS)
104 3.8.3Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.1 With Sulfur Anions (S2-, [HS-I) 1. G. Brauer, ed., Preparative Inorganic Chemistry, Enke Verlag, Stuttgart, 1975, pp. 1587 (green MnS), 1588 (red MnS), 1692 (NiS), 1667 (CoS). 2. (a) S. Dev, A. Taniguchi, T. Yamamoto, K. Kubota, Y. Tominaga, Colloid Polym. Sci., 265, 922 (1997); (b) K. Osaka, A. Taniguchi, E. Kubota, S. Dev, K. Tanaka, K. Kubota, T. Yamamoto, Chem. Muter., 4 , 562 (1992). 3. D. W. Rankin, Inorg. Synth., 15, 182 (1974). 4. R. R. Chianelli, M. B. Dines, Inorg. Chem., 17, 2758 (1978). 5. P. Bonneau, J. B. Wiley, R. B. Kaner, Inorg. Synth., 30, 33 (1995). 6. (a) K. Tatsumi, Y. Inoue, A. Nakamura, R. E. Cramer, W. VanDoorne, J. W. Gilje, J . Am. Chem. Soc., I l l , 782 (1989);(b) K. Tatsumi, Y. Inoue, H. Kawaguchi, M. Kohsaka, A. Nakamura, R. E. Cramer, W. VanDoorne, G . J. Taogoshi, P. N. Richmann, Organometallics, 12, 352 (1993). 7. (a) A. Muller, E. Diemann, R. Jostes, H. Bogge, Angew. Chern., Int. Ed. Engl., 20, 934 (1984); (b) A. Muller, E. Diemann, in Comprehensive Coordination Chemistry, Vol. 2, G. Wilkinson, R. D. Gillard, J. A. McCleverty, eds., Pergamon Press, Oxford, 1987, Vol. 2, p. 559. 8. Y. Do, E. D. Simhon, R. H. Holm, Inorg. Chem., 24,4635 (1985). 9. Y. Zhang, R. H. Holm, Inorg. Chem., 27, 3875 (1988). 10. J. W. McDonald, G. D. Friesen, L. D. Rosenhein, W. E. Newton, Inorg. Chim. Acta, 72,205 (1983). 11. T. Saito, Adv. Inorg. Chem., 44, 45 (1997). 12. K. Wieghardt, U. Bossek, B. Nuber, J. Weiss, Inorg. Chim. Acta, 126, 39 (1987). 13. (a) J. L. Deutsch, H. B. Jonassen, Inorg. Synth., 6, 170 (1962); (b) Y. Park, T. J. McCarthy, A. C. Sutorik, M. G. Kanatzidis, Inorg. Synth., 30, 88 (1992); (c) K. Klepp, H. Boller, Monatsh. Chem., 112, 83 (1981). 14. J.-F. You, B. S. Snyder, G. C. Papaefthymiou, R. H. Holm, J . Am. Chem. Soc., 112, 1067 (1990). 15. S. Rutchik, S. Kim, M. A. Walters, Inorg. Chem., 27, 1513 (1988). 16. P. R. Challen, S.-M. Koo, W. R. Dunham, D. Coucouvanis, J . Am. Chem. Soc., 112,2455 (1990). 17. L. Marko, J. Takacs, Inorg. Synth., 26, 243 (1989). 18. G. Brauer, ed., Preparative Inorganic Chemistry, Academic Press, New York, 1965, p. 1763. 19. T. B. Rauchfuss, T. D. Weatherill, Inorg. Chem., 21, 827 (1982). 20. (a) F. Cecconi, C. A. Ghilardi, S. Midollini, J . Chem. Soc., Chem. Commun., 640 (1981); (b) F. Cecconi, C. A. Ghilardi, S. Midollini, Inorg. Chim. Acta, 64, L47 (1981);(c) C. A. Ghilardi, S. Midollini, L. Sacconi, J . Chem. SOC., Chem. Commun.,640 (1981); (d) F. Cecconi, C . A. Ghilardi, S. Midollini, Inorg. Chem., 22,3802 (1983); (e)F. Cecconi, C. A. Ghilardi, S. Midollini, A. Orlandini, P. Zanello, Polyhedron, 5, 2021 (1986). 21. G. Christou, K. S. Hagen, J. K. Bashkin, R. H. Holm, Inorg. Chem., 24, 1010 (1985). 22. J. R. Lockemeyer, T. B. Rauchfuss, A. L. Rheingold, J . Am. Chem. Soc., 111, 5733 (1989). 23. A. Venturelli, T. B. Rauchfuss, J . Am. Chem. Soc., 116, 4824 (1994). 24. Y. Do, E. D. Simhon, R. H. Holm, Inorg. Chem., 24, 4635 (1985). 25. K. E. Howard, T. B. Rauchfuss, S. R. Wilson, Inorg. Chem., 27, 3561 (1988). 26. J. A. Kovacs, R. H. Holm, Inorg. Chem., 26, 702 (1987). 27. T. Shibahara, H. Akashi, Inorg. Synth., 29, 254 (1992). 28. T. Shibahara, H. Akashi, Inorg. Synth., 29, 260 (1992). 29. M.-C. Hong, Y.-J. Li, J. Lu, M. Nasreldin,A. G. Sykes, J . Chem. Soc., Dalton Trans., 2613 (1993). 30. D. Coucouvanis, A. Toupadakis, A. Hadjikyriacou, Inorg. Chem., 27, 3273 (1988). 31. D. Coucouvanis, A. Toupadakis, J. D. Lane, S. M. Koo, C. G. Kim, A. Hadjikyriacou, J . Am. Chem. Soc., 113, 5271 (1991). 32. V. W. Day, D. A. Lesch, T. B. Rauchfuss, J . Am. Chem. Soc., 104, 1290 (1982). 33 H. Liu, A. L. Tan, C. R. Cheng, K. F. Mok, T. S. A. Hor, Inorg. Chem., 36, 2916 (1997). 34. D. Coucouvanis, A. Salifoglou, M. G. Kanatzidis, A. Simopoulos, A. Kostikas, J . Am. Chem. Soc., 109, 3807 (1987). 35 J.-H. So, P. Boudjouk, Inorg. Synth., 29, 30 (1992). 36 M. J. Martin, G.-H. Qiang, D. M. Schleich, Inorg. Chem., 27, 2804 (1988). 37 V. Krug, G . Koellner, U. Muller, Z . Naturforsch., Teil B, 43, 1501 (1988). 38 D. Fenske, J. Ohmer, J. Hachgenei, K. Merzweiler, Angew. Chem., Int. Ed. Engl.,27,1277 (1988). 39. J. Darkwa, J. R. Lockemeyer, P. D. W. Boyd, T. B. Rauchfuss, A. L. Rheingold, J . Am. Chem. Soc., 110, 141 (1988). 40. W. G. Klemperer, C. Schwartz, Inorg. Chem., 24, 4461 (1985). 41. Y. Do, E. D. Simhon, R. H. Holm, Inorg. Chem., 24, 2827 (1985). 42. J. Sola, Y. Do, J. M. Berg, R. H. Holm, Inorg. Chem., 24, 1706 (1985).
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.2 With Polysulfido Anions (S;-) 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53.
105
S. C. Lee, J. Li, J. C. Mitchell, R. H. Holm, Inorg. Chem., 31, 4333 (1992). L. Cai, R. H. Holm, J . Am. Chem. Soc., 116, 7177 (1994). K. P. Callahan, P. J. Durand, Inorg. Chem., 19, 3211 (1980). V. P. Fedin, H. Imoto, T. Saito, V. E. Federov, Y. V. Mironov, S. S. Yarovoi, Polyhedron, 15, 1229 (1996). V. E. Federov, A. V. Mishchenko, V. P. Fedin, Russ. Chem. Reo., 54, 408 (1985). (a) D. M. Giolando, T. B. Rauchfuss, G. R. Clark, Inorg. Chem.,26,2080 (1987); (b) G. A. Zank, T. B. Rauchfuss, Organometallics, 3, 1191 (1984). (a) 0. M. Yaghi, Z. Sun, D. A. Richardson, T. L. Groy, J . Am. Chem. Soc., 116, 807 (1994); (b) A. Loose, W. S. Sheldrick, 2. Naturforsch., Teil B, 52, 687 (1997). R. W. Gingerich, R. J. Angelici, J . Am. Chem. Soc., 101, 5604 (1979). A. Shaver, G. Marmolejo, J. M. McCall, Inorg. Synth., 27, 65 (1990); (b) C. J. Ruffing, T. B. Rauchfuss, Organometallics, 3, 524 (1985). J. Amarasekera, T. B. Rauchfuss, Inorg. Chem., 28, 3875 (1989). H.-C. Liang, P. A. Shapley, Organometallics, 15, 1331 (1996).
3.8.3.6.2 With Polysulfido Anions (S:-)
(i) Synthesis of Binary Anions and Mixed Complexes. Salts of polysulfides, S:-, are mainly used for synthesis of polysulfido complexes from corresponding halides, but occasionally they give sulfido compounds: L,MX2
+ Si-
L,MSm
-2x-
e L,MS,
* LMSm-I -S
- nL
(a)
L,MS MS Polysulfide solutions form upon dissolving Ss, typically up to 5 equiv, in aqueous ammonium or alkali metal sulfide solutions. The average value of x in such Sy- solutions can be controlled, but it is usually not possible to control the value of y in MS, complexes, at least when they are prepared from ionic polysulfide reagents. Complementary to using polysulfide anions, and not discussed in this section, is reaction of S s with low-valent metal complexes and with metal thiolate complexes; the latter occur with elimination of organic disulfides. Reaction of alkali metal salts of S:- with Mn", Fe"', and Ni" halides gives polysulfides MnS:;, Fe2S:;, Nisi-, respectively'. Complexes of stoichiometry [M(S,),]"- exist for M = Rh, Ir, and Pt, although such complexes are sometimes obtainable in more sulfur-rich forms, i.e., with Sa- in place of S:- ligands as in IrS:; '. Palladium gives polymeric [Pd(S5)(p-S6)l2- Several polysulfido complexes are prepared under solvatothermal conditions, where reactants are heated in a sealed ampule with a small amount of solvent. Reactions often produce crystalline products even for poorly soluble species. Illustrative is reaction of K2S4 and K2PtCl, in the presence of H 2 0 to give, depending on reaction time, Pt4(p3-S),(S3);- o r Pt(S4)f '. Whereas ReS(S,); can be prepared more easily (e.g., from ReOi), its synthesis from Re2C1i- and Liz& illustrates polysulfide cleavage of a strong metal-metal interaction5. Representative structures for metal polysulfides are shown in Scheme 1.
'.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.2 With Polysulfido Anions (S;-) 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53.
105
S. C. Lee, J. Li, J. C. Mitchell, R. H. Holm, Inorg. Chem., 31, 4333 (1992). L. Cai, R. H. Holm, J . Am. Chem. Soc., 116, 7177 (1994). K. P. Callahan, P. J. Durand, Inorg. Chem., 19, 3211 (1980). V. P. Fedin, H. Imoto, T. Saito, V. E. Federov, Y. V. Mironov, S. S. Yarovoi, Polyhedron, 15, 1229 (1996). V. E. Federov, A. V. Mishchenko, V. P. Fedin, Russ. Chem. Reo., 54, 408 (1985). (a) D. M. Giolando, T. B. Rauchfuss, G. R. Clark, Inorg. Chem.,26,2080 (1987); (b) G. A. Zank, T. B. Rauchfuss, Organometallics, 3, 1191 (1984). (a) 0. M. Yaghi, Z. Sun, D. A. Richardson, T. L. Groy, J . Am. Chem. Soc., 116, 807 (1994); (b) A. Loose, W. S. Sheldrick, 2. Naturforsch., Teil B, 52, 687 (1997). R. W. Gingerich, R. J. Angelici, J . Am. Chem. Soc., 101, 5604 (1979). A. Shaver, G. Marmolejo, J. M. McCall, Inorg. Synth., 27, 65 (1990); (b) C. J. Ruffing, T. B. Rauchfuss, Organometallics, 3, 524 (1985). J. Amarasekera, T. B. Rauchfuss, Inorg. Chem., 28, 3875 (1989). H.-C. Liang, P. A. Shapley, Organometallics, 15, 1331 (1996).
3.8.3.6.2 With Polysulfido Anions (S:-)
(i) Synthesis of Binary Anions and Mixed Complexes. Salts of polysulfides, S:-, are mainly used for synthesis of polysulfido complexes from corresponding halides, but occasionally they give sulfido compounds: L,MX2
+ Si-
L,MSm
-2x-
e L,MS,
* LMSm-I -S
- nL
(a)
L,MS MS Polysulfide solutions form upon dissolving Ss, typically up to 5 equiv, in aqueous ammonium or alkali metal sulfide solutions. The average value of x in such Sy- solutions can be controlled, but it is usually not possible to control the value of y in MS, complexes, at least when they are prepared from ionic polysulfide reagents. Complementary to using polysulfide anions, and not discussed in this section, is reaction of S s with low-valent metal complexes and with metal thiolate complexes; the latter occur with elimination of organic disulfides. Reaction of alkali metal salts of S:- with Mn", Fe"', and Ni" halides gives polysulfides MnS:;, Fe2S:;, Nisi-, respectively'. Complexes of stoichiometry [M(S,),]"- exist for M = Rh, Ir, and Pt, although such complexes are sometimes obtainable in more sulfur-rich forms, i.e., with Sa- in place of S:- ligands as in IrS:; '. Palladium gives polymeric [Pd(S5)(p-S6)l2- Several polysulfido complexes are prepared under solvatothermal conditions, where reactants are heated in a sealed ampule with a small amount of solvent. Reactions often produce crystalline products even for poorly soluble species. Illustrative is reaction of K2S4 and K2PtCl, in the presence of H 2 0 to give, depending on reaction time, Pt4(p3-S),(S3);- o r Pt(S4)f '. Whereas ReS(S,); can be prepared more easily (e.g., from ReOi), its synthesis from Re2C1i- and Liz& illustrates polysulfide cleavage of a strong metal-metal interaction5. Representative structures for metal polysulfides are shown in Scheme 1.
'.
106 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.2 With Polysulfido Anions (S:-)
The synthesis of mixed ligand polysulfido complexes is well developed. Solutions of (C5H5)2MC12(M = Ti, V, Mo, W) and S:- react to give (C5H&MS5 (M = Ti, V) and (C,H5)2MS4 (M = Mo, W)?
Several (C5Me5)Repolysulfides form by addition of Na2S4 to (C5Me5)ReC14, producing sequentially (C5Me5)ReS3C12and (C,Me,)Re(S3)(S4).Both adopt piano-stool geometries7. Organometallic oxides also are reactive toward polysulfide solutions: e.g., reaction of (C,Me,) ReO(S4) with S:- gives (C5Me,) Re(S3)(S4)’. Weakly bound (PF6)2are displaced by “Si-’’ to acetonitrile ligands in [(C5H5)2Fe2(SEt)2(CH3CN)2] give (C5H5)zFe2(SEt)2S29:
L
L
I
s2-2L
I Et
/s-s ,FeCp ‘
CpFe,
’ssI( I
Et
Et
Et
(4
Polysulfide chemistry also ties in with the Fe-S-SR system, although most clusters in this family are derived by oxidation ofiron thiolates with S8 or by reaction of SH-, SR-, and FeC13. Treatment of “Fe(SCH2Ph)3”with Na2S2 yields the cluster Fe6S6(SCH2Ph)i-lo:
Mixed ligand polysulfido complexes of Ir are also prepared by metathetical reactions; e.g., from (C5Me,)Ir(PMe3)Clzone can obtain (C,Me5)Ir(PMe3)S, (x = 4, 5,6)”. (ii) Formation of Metal Polysulfido Complexes from Thiometallates. Thiomolybdates and related compounds are widely employed as precursors to di- and polysulfido complexes. The salts (NH4),MoS4 and (NH4)3VS4thermally decompose to MoS3 and V2s5, respectively”: H2S 2NH3 ( N H ~ ) ~ M o S ~ MoS3 (f)
+
+
Heating (NH4)3VS4solutions in the presence of the tridentate ligand terpyridine (terpy) yields V ( t e r p ~ ) ( S ~Quaternary ) ~ ~ ~ . ammonium salts of MoSi-, react with sulfur donors such as (PhCH2)2S3to give (PPh4),Mo2S, (x = 10-12). These [Mo”I2 compounds undergo desulfurization by PPh3 to MO&-, which in turn can be sulfurized to give Mo2S:-, Mo&, or Mo&- (Scheme 2)14.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 107 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.2 With Polysulfido Anions ( S $ - )
Scheme 2 Related compounds are obtained when the terminal sulfido atoms are replaced by oxide. Families of Mo-NO-S clusters are prepared by poorly defined routes using mixtures of H2S, NH,OH, and alkali metal molybdates15. Reaction of ammonium polysulfide with R e 0 4 is complex, giving ReSi and a variety of structurally unusual species, including Re4S4&)2- and Re2(~-S)2(~-S3)2(S4):-.
(iii) Formation of Metal Polysulfido Complexes Using Anhydrous S$- Sources. Mixtures of s8 and alkali metal sulfides are effective reagents for synthesis of ternary phases starting from metals and metal sulfides. Such "reactive fluxes" are good solvents, facilitating crystal growth and offering oxidizing equivalents through the agency of the S-S bonds. Melting points of alkali metal polysulfides are well below those of the sulfide: compare Na2S3 (mp. 229°C) and NazS (m.p. 1080°C)16.Illustrative is the reaction of K2S, with Ti and Ta, yielding the solid materials K4Ti33S14and K4Ta2S11at reaction temperatures of 375 and 800'C, respectively". Anhydrous solutions of lithium polysulfides are obtained by reduction of T H F suspensions of sulfur with LiBHEt3: 2LiBHEt3 + xS-
THF
Li2S,2BEt3
+ H2
(g)
Unlike Li2S,, Li2S,, 2BEt3 forms homogeneous solutions in THF, allowing greater control of reactions, provided BEt, does not interfere with the syntheses. These anhydrous polysulfide reagents are employed in preparation of (C5H5)2MS5 (M = Zr, Hf) and (C5Me5)2TiS3from corresponding dichlorides". The related reaction of CpTiC13 with LizS2.xBEt3 affords 0x0-centered clusters Cp4Ti&O; the oxygen source was not identified, but since two groups made similar Ti-oxo chalcogenide clusters, it appears that intermediates in this reaction are extremely o x ~ p h i l i c ' ~ . Addition of quaternary ammonium salts to aqueous polysulfide solutions precipitates salts of formula (ER4)2Sx(ER,' = PPh; or NBu; and x = 6)20. These salts are soluble in polar organic solvents such as MeCN and DMF, but in solution they reversibly fragment into deeply colored radical anions S, and S;. Nevertheless, these salts are useful sources of polysulfide complexes. Polysulfides of Ru have been prepared by reaction of (NBUq)& with (C5H5)Ru(PPh3): sources, giving (C5H5)2R~Z(PPh3)2(Sx)2 (x = 2, 3 ) 2 1 .
108 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.2 With Polysulfido Anions (S:- ) (iv) Formation of Metal Polysulfido Complexes Using Sf- Transfer Reagents. Several metal sulfides form by transfer of a polysulfido ligand from one transition metal to another. Two complexes that show particular promise are CpzTiS5 and ZnS,(TMEDA). The Zn complex, prepared by direct reaction of Zn, TMEDA, and s8, reacts with Cp2TiC12yielding Cp2TiS522.Treatment of (C5Me5)ReOC12with CpzTiS5 gives the tetrasulfide (C5Me50)ReO(S4).That the product is not a pentasulfide again illustrates the facility of ring contraction (and expansion) reactions for metal polysulfido complexesz3.Similarly, rection of Cp2TiS5with Ti(P)F2 (and Ti(P)F) affords Ti(P)(Sz), where P is the dianion of a p ~ r p h y r i n ~ ~ . -S
vj
Ti(porphyrinate)F2
+
Cp2TiS5
-Cp,TiF, -3 s
(h)
)
\
N
-
/
(v) Formationof Metal Polysulfido Complexes Via the Oxidative Decarbonylation Reaction. Many metal sulfides and polysulfides are prepared by “oxidative decarb ~ n y l a t i o n5”, ~a method involving treatment of metal carbonyl compounds with polysulfide anions. Reaction of (C5Me5)Mo(CO),CH3with KzS4 gives (C5Me5)Mo(C0)2S; followed by (C5Me5)Mo(S4)(S2CO)-. From W(CO)6,Mo(CO),, Cr(CO),, and Mnz(CO)lo are obtained, respectively, WS:-, MoSi-, Cr(S2CO):-, and Mnz(S4),(CO);-:
-
+ ‘‘S’-” M O ( C O ) ~- 6 COS MOS: -
(4
These reactions appear to proceed via nucleophilic attack of a polysulfido anion on coordinated CO initially giving dithiocarbonato complexes. Reaction of methylimidazole (MeIm) solutions of S8 with metal powders (or metal carbonyls) gives salts of type [M(MeIrn),]’+Si- (M = Mg, Mn, Fe, Ni). The salts can be used in synthesizing polysulfido complexes by reaction with metal carbonyls; e.g., reaction of [Ni(MeIrn),]’ + $ - ,s8 and Fe(CO)5 results in oxidative decarbonylation to [Ni(MeIm)g ‘1 [Fez (/L-S)~(S~); -Iz6.
(T.B. RAUCHFUSS)
1. (a) M. E. Draganjac, T. B. Rauchfuss, Angew. Chem., Int. Ed. Engl., 24, 742 (1985); (b) E. Diemann, in Comprehensive Coordination Chemistry, Vol. 5, G. Wilkinson, R. D. Gillard, J. A. McCleverty, eds., Pergamon Press, Oxford, 1987; (c) A. Muller, E. Diemann, Ada. Inorg. Chem., 31, 89 (1987). 2. T. E. Albrecht-Schmitt, J. A. Ibers, Inorg. Chem., 35, 7273 (1996). 3. R. A. Krause, A. Wickenden Kozlowski, J. L. Cronin, Inorg. Synth., 21,12 (1982) (Note, however, that the claimed synthesis of Pt(S,):- in this paper is suspect, see work of Kim and Kanatzidis, ref. 4). 4. K.-W. Kim, M. G. Kanatzidis, Inorg. Chem., 32, 4161 (1993). 5. F. A. Cotton, P. A. Kibala, M. Matusz, Polyhedron, 7, 83 (1988). 6. J. Darkwa, D. M. Giolando, C. J. Murphy, T. B. Rauchfuss, Inorg. Synth., 27, 51 (1990). 7. M. Herberhold, G.-X. Jin, W. Milius, Z. Anorg. Allg. Chem., 620, 299 (1994). 8. M. Herberhold, G.-H. Guo, W. Milius, Angew. Chem., Int. Ed. Engl., 32, 85 (1993). 9. G. J. Kubas, P. J. Vergamini, Inorg. Synth., 21, 37 (1982). 10. H. Strasdeit, B. Krebs, G. Henkel, Inorg. Chem., 23, 1816 (1984). 11. M. Herberhold, G.-X. Jin, A. L. Rheingold, Chem. Ber., 124, 2245 (1991).
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 109 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RS]S. P. Cramer,K. S. Liang, A. J. Jacobson, A. J. Chang, R. R. Chianelli, Inorq. Chem., 23,1215 (1984). F. T. Al-Ani, D. L. Hughes, C . J. Pickett, J . Chem. Soc., Dalton Trans., 1705 (1988). A. I. Hadjikyriacou, D. Coucouvanis, Inorq. Synth., 27, 39 (1990). A. Miiller, W. Eltzner, N. Mohan, Angew. Chem., Int. Ed. Enql., 18, 168 (1979). (a) M. G. Kanatzidis, A. C. Sutorik, Prog. Inorg. Chem., 43, 151 (1995); (b) W. S. Sheldrick, M. Wachold, Angew. Chem., Int. Ed. Enql., 36, 206 (1997). 17. (a) S. A. Sunshine, D. Kang, J. A. Ibers, Inorq. Synth., 30, 85 (1995); (b) S. Schreiner, L. E. Aleandri, D. Kang, J. A. Ibers, Inorq. Chem., 28, 392 (1989). 18. A. Shaver, J. M. McCall, G. Marrnolejo, Inorq. Synth., 27, 59 (1990). 19. (a) G. A. Zank, C. A. Jones, T. B. Rauchfuss, A. L. Rheingold, Inorq. Chem., 25, 1886 (1986); (b) P. G. Maue, D. Fenske, Z. Naturforsch., Teil B, 43, 1213 (1988). 20. (a) M. Schnock, P. Bottcher, Z . Naturforsch., Teil B, 50, 721 (1995); (b) C. Miiller, P. Bottcher, Z . Naturforsch., Teil B, 49, 489 (1994). 21. J. Amarasekera, T. B. Rauchfuss, A. L. Rheingold, Inorg. Chem., 26, 2017 (1987). 22. A. K. Verrna, T. B. Rauchfuss, Inorq. Chem., 34, 6911 (1995). 23. J. Kulpe, E. Herdtweck, G. Weichselbaumer, W. A. Herrmann, J . Orqanometal. Chem., 348,369 (1988). 24. H. Brand, J. Arnold, Coord. Chem. Ret;., 140, 137 (1995). 25. J. W. Kolis, Coord. Chem. Rev., 105, 195 (1990). 26. T. B. Rauchfuss, S. Dev, S. R. Wilson, Inorq. Chem., 31, 153 (1992). 12. 13. 14. 15. 16.
3.8.3.6.3 With Organosulfur Anions [RSl-
(i) General Comments. Four factors are important in the synthesis of M-S bonds from thiolate anions: (1)high nucleophilicity of thiolate anions facilitates displacement of halide ligands; ( 2 ) reducing power of thiolates often effects reduction of the metal center (concomitant with formation of the disulfide, R2S2); (3) enhanced basicity of thiolate ligands often leads to thiolato-bridge species of higher nuclearity; and (4) the C-S bond often undergoes scission to sulfides. The latter is important for early transition metal thiolates, especially for benzylthiolates, t-butylthiolates, and ethanedithiolates. (ii) Homoleptic Metal Thiolales’. Complex Mo(SBU‘)~is prepared from MoCl, and LiBu‘, to be contrasted with synthesis of the Ti analogue from the thiol and Ti(NEt2)42.The coordinatively unsaturated Mo(1V) species reacts with ligands, giving rearrangement products3. More typically, M(SR), compounds are insoluble polymers [e.g., Cr(SR),] and the neutral thiolates of Ni(II), Pd(II), and Pt(I1). Neutral M2[SC6H22,4,6-(t-B~)~],( M = Mn, Fe), rare examples of neutral homoleptic thiolates, not to mention tricoordination, form from the bulky thiol and M[N(SiMe3)2]24. For the Ni-SEt system, the soluble hexamer [Ni(SEt)J6, which consists of a cyclic array of SEt-bridged, square-planar Ni(I1) subunits, can be isolated5. The second family of simple thiolato complexes comprises anions of formula M(SR)r-. These are numerous and often prepared simply by addition of excess of thiolate salt to a solution of metal halide. Addition of excess [PhS]- to chloride or xanthate complexes of divalent metals gives tetrahedral complexes [M(SPh),12-, which are isolated as their crystalline Ph4P+ salts (M = Mn, Fe, Co, Zn, Cd)6. Monometallic homoleptic thiolato complexes often exist in equilbrium with species of higher nuclearity; e.g., equilibria involving [M(SR),]’-, [M2(SR),]’-, and [M4(SR),o]2- are important for Fe(I1) and Co(I1). Intercoversion chemistry is well worked out for Fe; the major complication is the occurrence of redox reactions, since Fe(II1) thiolates are often unstable. Corresponding homoleptic 1,2-ethanedithiolates (edt) are known for Ti(edt)i Vz(edt)i-, Cr(edt):-, Mn(edt):-, Mn2(edt)i-, Fe2(edt)i-, Co(edt):-, Ni2(edt):-; all of which form from Nazedt and metal halides’.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 109 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RS]S. P. Cramer,K. S. Liang, A. J. Jacobson, A. J. Chang, R. R. Chianelli, Inorq. Chem., 23,1215 (1984). F. T. Al-Ani, D. L. Hughes, C . J. Pickett, J . Chem. Soc., Dalton Trans., 1705 (1988). A. I. Hadjikyriacou, D. Coucouvanis, Inorq. Synth., 27, 39 (1990). A. Miiller, W. Eltzner, N. Mohan, Angew. Chem., Int. Ed. Enql., 18, 168 (1979). (a) M. G. Kanatzidis, A. C. Sutorik, Prog. Inorg. Chem., 43, 151 (1995); (b) W. S. Sheldrick, M. Wachold, Angew. Chem., Int. Ed. Enql., 36, 206 (1997). 17. (a) S. A. Sunshine, D. Kang, J. A. Ibers, Inorq. Synth., 30, 85 (1995); (b) S. Schreiner, L. E. Aleandri, D. Kang, J. A. Ibers, Inorq. Chem., 28, 392 (1989). 18. A. Shaver, J. M. McCall, G. Marrnolejo, Inorq. Synth., 27, 59 (1990). 19. (a) G. A. Zank, C. A. Jones, T. B. Rauchfuss, A. L. Rheingold, Inorq. Chem., 25, 1886 (1986); (b) P. G. Maue, D. Fenske, Z. Naturforsch., Teil B, 43, 1213 (1988). 20. (a) M. Schnock, P. Bottcher, Z . Naturforsch., Teil B, 50, 721 (1995); (b) C. Miiller, P. Bottcher, Z . Naturforsch., Teil B, 49, 489 (1994). 21. J. Amarasekera, T. B. Rauchfuss, A. L. Rheingold, Inorg. Chem., 26, 2017 (1987). 22. A. K. Verrna, T. B. Rauchfuss, Inorq. Chem., 34, 6911 (1995). 23. J. Kulpe, E. Herdtweck, G. Weichselbaumer, W. A. Herrmann, J . Orqanometal. Chem., 348,369 (1988). 24. H. Brand, J. Arnold, Coord. Chem. Ret;., 140, 137 (1995). 25. J. W. Kolis, Coord. Chem. Rev., 105, 195 (1990). 26. T. B. Rauchfuss, S. Dev, S. R. Wilson, Inorq. Chem., 31, 153 (1992). 12. 13. 14. 15. 16.
3.8.3.6.3 With Organosulfur Anions [RSl-
(i) General Comments. Four factors are important in the synthesis of M-S bonds from thiolate anions: (1)high nucleophilicity of thiolate anions facilitates displacement of halide ligands; ( 2 ) reducing power of thiolates often effects reduction of the metal center (concomitant with formation of the disulfide, R2S2); (3) enhanced basicity of thiolate ligands often leads to thiolato-bridge species of higher nuclearity; and (4) the C-S bond often undergoes scission to sulfides. The latter is important for early transition metal thiolates, especially for benzylthiolates, t-butylthiolates, and ethanedithiolates. (ii) Homoleptic Metal Thiolales’. Complex Mo(SBU‘)~is prepared from MoCl, and LiBu‘, to be contrasted with synthesis of the Ti analogue from the thiol and Ti(NEt2)42.The coordinatively unsaturated Mo(1V) species reacts with ligands, giving rearrangement products3. More typically, M(SR), compounds are insoluble polymers [e.g., Cr(SR),] and the neutral thiolates of Ni(II), Pd(II), and Pt(I1). Neutral M2[SC6H22,4,6-(t-B~)~],( M = Mn, Fe), rare examples of neutral homoleptic thiolates, not to mention tricoordination, form from the bulky thiol and M[N(SiMe3)2]24. For the Ni-SEt system, the soluble hexamer [Ni(SEt)J6, which consists of a cyclic array of SEt-bridged, square-planar Ni(I1) subunits, can be isolated5. The second family of simple thiolato complexes comprises anions of formula M(SR)r-. These are numerous and often prepared simply by addition of excess of thiolate salt to a solution of metal halide. Addition of excess [PhS]- to chloride or xanthate complexes of divalent metals gives tetrahedral complexes [M(SPh),12-, which are isolated as their crystalline Ph4P+ salts (M = Mn, Fe, Co, Zn, Cd)6. Monometallic homoleptic thiolato complexes often exist in equilbrium with species of higher nuclearity; e.g., equilibria involving [M(SR),]’-, [M2(SR),]’-, and [M4(SR),o]2- are important for Fe(I1) and Co(I1). Intercoversion chemistry is well worked out for Fe; the major complication is the occurrence of redox reactions, since Fe(II1) thiolates are often unstable. Corresponding homoleptic 1,2-ethanedithiolates (edt) are known for Ti(edt)i Vz(edt)i-, Cr(edt):-, Mn(edt):-, Mn2(edt)i-, Fe2(edt)i-, Co(edt):-, Ni2(edt):-; all of which form from Nazedt and metal halides’.
110 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RSI-
(iii) M-S-SR Systems. C-S bond cleavage was observed in attempts to prepare Ti(1V) complexes from (LiSC2H4)2Sand TiCl,, which gives Ti(edt):- '. Reaction of t-BUSH with Zr(BH4), gives Zr3S3(t-B~S)2(BH4)4(THF)2 and the related double triangle cluster Zr6S6(t-B~S)4(BH4)x(THF)2. This also illustrates use of metal borohydrides as nontraditional alternatives to metal halides in metathesis reactions. Similarly, starting with tBuSH and Zr(CH,Ph), one obtains Z T ~ ( ~ ~ - S ) ( S sulfide B U ~ ) formation ~~; is explained by observation of coproduct isobutene, (CH3)2C=CH29:
+ 3Zr(CH2Ph),-
llt-BUSH
+
Z ~ , ( S ) ( S B U ~ Me2C=CH2 )~~
+ 12PhCH3
(a)
Facile C-S bond cleavage processes also seen in reactions of LiS-t-Bu, Sg, and NbC15 in the presence of Et,NCl, which, depending on conditions, gives salts of NbS(SBu'), , NbS2(SBu');, or NbS3(SBut)'- l o , Fragmentation of ethanedithiolate ligands in Nb(edt), occurs with heating, resulting in migration of a C2H4 unit to give NbS(edt)(SC2H4SC2H4S)Salts of general stoichiometry Fe,(SR),Sc- are prepared by many routes, most of which employ thiolates and an Fe(II1) salt (which often is reduced in the process)'2. The adamantoid cage Fe,(SR):, is oxidized by S8 giving, depending on conditions and reactant ratios, [Fe2S2(SR)4]2-, [Fe3S4(SR),l3-, [Fe,S,(SR),l2-, or [Fe6S,(SR),l4- 13. The organic substituent also influences the course of these interconversions; e.g., EtS-allows isolation of Fe(II1)-rich species',, whereas the less basic PhSfavors more reduced s p e ~ i e s ' ~Some . interconversions are depicted in Scheme 1. RS RS-Fe RS
2-
I
SR
SR '
excess SR-
____$
SF
RS
+s/
R
i;
ts -RA
-RA
rRS
1
2-
Y
-R2Sz
Scheme 1
2-
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 111 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RSI~~~~
~
Isolation of these black or dark brown, air-sensitive materials is facilitated by quaternary ammonium counterions. Complementary preparations of sulfido thiolato clusters employ the soluble S-atom transfer agent (PhCH,S),S (prepared via reaction of PhCH2SH and SClz in petroleum solvents). An efficient, one-pot route to Fe4S4(SPh)i- involves reaction of LiOMe with PhSH, FeC13, followed by reoxidation with elemental sulfurI6. Although less developed than the Fe-S-SR system, sulfido thiolates are also well known for c o and N< e.g., reaction of [ C O ~ ( S R ) ~with ~ ] ~ sulfur gives [ C O ~ S ~ ( S R ) , ] ~ - , which can be contrasted with [Co6S8(PEt3),14' obtained in the Co-H2S/PEt3 system (3.8.3.6.2). Several Ni-S-SR clusters are prepared by both addition of S8 to nickel thiolates and S extrusion from thiolates. The latter process is shown by treatment of NiC12 with LiS-t-Bu, yielding the reduced cluster Ni5S(SBu');. When the related reaction is conducted in the presence of CN-, the Ni(I1) is not reduced; instead, Ni3S(SB~')3(CN)32formsI7. Several chelating thiolates have been employed in studies of the Fe-S-SR compound family (Scheme 2). a,&'-Xylenedithiolate stabilizes tetrahedral thiolato complexes by means of its wide bite angle, exemplified in the unusual cluster -. Other thiolates can be installed that engage the thiolate {Fe3S[C6H4(CHzS)2]3}Z sulfur in strong hydrogen bonds". In [Fe4S4(SR),I2-, the four thiolates undergo exchange at the same rate, which thwarts site-selective reactions. Exchange rates of three of the four sites can be suppressed using trithiols based on C6R3-2,4-6-(3-C6H4SH)3, which binds to three of the four terminal sites of Fe4Si' clusterslg.
Scheme 2
w
(iv) Other Metal Thiolates. Bis(cyclopentadieny1)metal dihalides of Ti, Nb, Mo, and W react with [RS] -, or more commonly Et3NH'RS-, giving the corresponding derivatives, (CsHs)2M(SR)22 0 . Titanium thiolates have received special attention because they react with electrophilic halides (e.g., CSC1,) to give back Cp,TiClz and the modified sulfur ligand [e.g., (RS)2CS].Z1The compounds (CsHs),M(SR), function as chelating ligands for other metal ions:
(M =Ti, Nb, Mo)
Whereas (CSHs)2V(SPh)2 forms by the oxidation of (CSH&V by Ph2S2,direct reaction of NaSPh with (C5H5)2VC12yields dimer (CsH5)zVz(SPh)4. Reaction of HS'Bu with chromocene gives dark violet paramagnetic crystalline (CsHs)2Cr2(StBu)ZS ". As with thiols in (C5H&Ni reactions, this reaction involves use
1 1 2 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RSI-
of C5H5 as an internal base; the coproduct is C5H6. This procedure highlights the preparative advantages of t-butylmercaptan as a sulfide source. The (C5H5)zCrz(S‘Bu)zS is a versatile precursor to heterometallic thiolato clusters and has a rich coordination chemistry. More complex CpM thiolates are common. (C5H5)zCrz(SR)z(N0)z can be prepared from metathetical reactions involving (C5H5)Cr(N0)zCl. Oxometal thiolato derivatives, which are well known for the early transition metals, are typically prepared by treatment of 0x0 and alkoxo complexes and free thiols (with concomitant elimination of H z O and ROH). Oxometal chloride complexes are commonly employed also; e.g., MoOCl,(THF) reacts with Et,NH+PhS- giving [MoO(SPh),] -, while the more nucleophilic alkylthiolate salt Et3NH+PhCHzS-reacts with [MoOC14(OHz)]- yielding the reduction product [MoZO2(SCHzPh),)]- 2 3 . Active site models for 0-atom transfer enzymes are prepared by reaction of thiols with MoOz(acac)z;the acac- ion serves as a proton acceptorz4.Aqueous sodium molybdate reacts with cysteine (cysHz) to give a yellow precipitate of dioxo-bridged dimer M ~ ~ O ~ ( p - O ) ~ ( The c y s aquo ) ~ . ligands in M O ~ O ~ S ~ ( undergo H ~ O ) substitution ~ ~ by cysteinate giving Moz0zSz(cysz)2”. A m ore controlled synthetic approach to oxometallothiolates involves derivatives of simple oxometallates [e.g., Moz04(EtzNCSz)z],which react with thiols giving dimers that contain p - S R groups. Other Mo-thiolates form by oxidative addition of thiols to Mo(0) complexesz6. Fragmentation of the bond between tertiary carbon and sulfur occurs when WC16 is treated with Me3SiSBu’,yielding WSC1, and ‘BuC1”. A variation of this involves reaction of (C5Me5)WC14and LizCzH4Szgiving (C5Me5)WS;, isolated as its P P h t salt”: (C5Me5)WC14+ 2.5LiZCZH4S2-
(C5Me5)WS;
+ 2C2H4 + 4LiCl
+ 0.5CzH4Sz + S
(4
Both halide and CO undergo displacement upon treatment of M(CO)5X(M = Re, Mn; X = Cl, Br) with [RSl-, a reaction that gives M2(SR)z(CO)s.Alternatively, Bu3SnSPh reacts with Mn(CO),Br and E ~ , N [ M ~ I ~ B ~ ~ (giving C O ) ~the ] neutral dimer and Et4N[Mnz(sPh),(Co),], respectively. Pertechnetate, [TcO,]-, is reduced by thiols to pentavalent derivatives, [TcO(SR),] -. Related 0x0 and nitrido thiolates of Ru and 0 s are prepared from the corresponding metal 0x0 and nitrido halides2’. Simple four-coordinate Fe(I1) thiolates of the type Fe(SR)zLz,where L is a tertiary phosphine or methylimidazole (MeIm), form in metathetical reactions3’: FeClz
+ 2NaSAr + 2MeIm-
Fe(SAr)2(Melm)z+ 2NaCl
(4
The most widely studied nitrosyl-thiolato complexes are of type Fez(SR)2(N0)4,obtained in good yield from reaction of Fe(I1)salts, mercaptans, and NO, or by alkylation of [FezSz(NO)4]Z-.A versatile preparative route to Fe nitrosyl thiolates uses FeZI2(NO),, easily prepared from Fe metal, I z , and NO (Scheme 3). Fe(H20)?
+
4RS-
+
Fe2S2(NO)i- t 2RX Fe212(N0)4 + 2RS-
4N0
R ( 0 N ) 2 F e AFe(N0)2 ’S‘
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 113 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RSI-
Co,I,(NO), reacts with thiolate anions giving, CO~(SR)~(NO),~’. Iron(II1) chloride derivatives of tetraazamacrocycles (N4) react with [RS] - forming the compounds Fe(N,)(SR). Analogous Fe(II1) porphyrin thiolates form by this route as well as by treatment of [Fe(porphyrinate)],O with the free thiols, with elimination of H 2 0 . These Fe(II1) complexes are most stable for electronegatively substituted thiols3’. Cyclopentadienyl metal carbonyl halides, (C5H5)Fe(C0),X and (C5H5)Mo(C0)3X, react with and (C5H5)2Fe2(C0)2(SR)2, which are also [SR] - giving dimers (C5H5)2M02(CO)2(SR)2 prepared via oxidative addition employing organic disulfides. Performing this reaction under mild conditions or employing perfluorinated thiolates (e.g. AgSC6F5)results in simple halide displacement. The dimers are stable solids; they adopt several geometries depending on the disposition of cyclopentadienyl groups and substituents on sulfur. The complex [Ru(NH3),(RSH)12’, prepared from corresponding [Ru(NH3), (H20)]” and RSH, can be reversibly d e p r ~ t o n a t e d ~Organometallic ,. Ru thiolates are prepared from (C5Me5)2R~ZC14 or (C5Me5),Ru4C14and thiolates, which give derivatives (C,Me5),Ru2(SR), ( n = 2,3, or 4)34. Although otherwise relatively rare, metal-thiolato-olefin complexes form readily from M2C12(COD)2(M = Rh, Ir; COD = 1,5-cyclooctadiene) and the thiolates giving M2(SR)2(COD)2.These compounds have preparative value because the diolefin is displacable by other ligands such as CO and tertiary p h o ~ p h i n e sIn ~ ~a. related conversion, Rh2C12(C0)4and Ir2C12(C0)6react with NaSR giving dimers M2(SR)2(C0)4;with the Rh-S‘Bu system, intermediate Rh,(S‘Bu)(Cl)(CO), is isolated. Rh2(SBu‘),(C0), undergoes CO displacement thermally by phosphites to give R ~ , ( S B U ‘ ) ~ ( C O ) ~ [P(OMe),],; the corresponding phosphite complex Rh2(SBu‘)2[P(OMe)3]4forms by with addition of LiSBu‘ to RhzC12[P(OMe)3]436.Treatment of tr~ns-IrCl(CO)(PPh~)~ NaSR gives air-sensitive, yellow tr~ns-1r(SR)(CO)(PPh,),~’. The chemistry of nickel thiolates is synthetically straightforward; for this reason nickel is used to test coordinating properties of many thiolato ligands,’. Mercaptans react with Ni(C,H,), to give black, air-stable dimers, Ni2(C5H5),(SR),: 2Ni(C,H5),
+ 2RSH-
Ni2(C5H5),(SR)2
+ 2C5H6
(4
Metatheses of chloro complexes provide routes to Pt metal phosphine thiolates. Without strongly basic or chelating ligands, such processes are complicated by formation of thiolate-bridged dimers and oligomers. Pt(SR)2(PR3)2 is prepared from PtC12(PR3)2,but the p-chloro Pt dimers of alkylphosphines react with NaSR giving stable p-thiolato derivatives. Comparable chemistry with 1,2-ethanedithiolate is observed (Scheme 4)39.
’
u
S
Scheme 4
S‘ ’
‘PPh3
114 3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.6 Sulfur Anions-Transition and Inner Transition Metal Bonds 3.8.3.6.3 With Organosulfur Anions [RSI-
[PtCl(terpy)] (terpy = terpyridyl) is used to prepare monodentate (S-bond) derivatives of mercaptoethanol and mercaptoethylamine by metathesis4'. +
(v) Specialized Thiolato Ligands. Complexing properties of numerous complicated or bulky4' thiolates have been examined, usually in some biological context. Some ~ , Ni46chelate complexes are shown in Scheme 5; examples of Ti4', T c ~M~ o, ~R~u, ~and all are prepared from a thiolate salt in metathetical reactions with the chlorides.
EtO'
Scheme 5
OEt
(T. B. RAUCHFUSS)
1 . I. G. Dance, Polyhedron, 5, 1037 (1986). 2. (a) J. Cheon, J. E. Gozum, G. S. Girolami, Chem. Muter., 9, 1847 (1997); (b) E. Roland, E. C. Walborsky, J. C. Dewan, R. R. Schrock, J . Am. Chem. Soc. 107, 5795 (1985); (c) N. Ueyama, H. Zaima, A. Nakamura, Chem. Lett., 1481 (1985); (d), J. R. Dilworth, P. T. Bishop, D. L. Hughes, J . Chem. Soc., Dalton Trans., 2535 (1988). 3. S. Otsuka, M. Kamata, K. Hirotsu, T. Higuchi, J. Am. Chem. SOC.,103, 3011 (1981). 4. P. P. Power, S. C. Shoner, Angew. Chem., Int. Ed. Engl., 30, 330 (1991). 5. P. G. Woodward, L. F. Dahl, E. W. Abel, B. C. Crosse, J . Am. Chem. SOC.,87, 5251 (1965). 6 . D. Coucouvanis, C. N. Murphy, E. Simhon, P. Stremple, M. Draganjac, Inorg. Synth., 21, 23 (1982). 7. Ch. P. Rao, J. R. Dorfman, R. H. Holm, Inorg. Chem., 25, 428 (1986). 8. H. Kawaguchi, K. Tatsumi, A. Nakamura, J . Chem. SOC.,Chem. Commun., 111 (1995). 9. D. Coucouvanis, A. Hadjikyriacou, R. Lester, M. Kanatzidis, Inorg. Chem., 33, 3645 (1994). 10. D. Coucouvanis, S.-J. Chen, B. S. Mandimutsira, C. G. Kim, Inorg. Chem., 33, 4429 (1994). 11. K. Tatsumi, Y. Sekiguchi, A. Nakamura, R. E. Cramer, J. J. Rupp, J . Am. Chem. SOC., 108, 1358 (1986). 12. B. Krebs, G. Henkel, Angew. Chem., Int. Ed. Engl., 30, 769 (1991). 13. H. Beinert, R. H. Holm, E. Miinck, Science, 277, 653 (1997). 14. K. S. Hagen, A. D. Watson, R. H. Holm, J . Am. Chem. SOC.,105, 3905 (1983). 15. K. S. Hagen, J. G. Reynolds, R. H. Holm J . Am. Chem. SOC.,103, 4054 (1981). 16. G. Christou, C. D. Garner, A. Balasubramanian, B. Ridge, H. N. Rydon, Inorg. Synth., 21, 33 (1982). 17. A. Miiller, G. J. Henkel, J . Chem. SOC.,Chem. Commun., 1005 (1996). 18. N. Ueyama, Y. Yamada, T. Okamura, S. Kimura, A. Nakamura, Inorg. Chem., 35, 6473 (1996). 19. R. H. Holm, S. Ciurli, J. A. Weigel, Prog. Inorg. Chem., 38, 1 (1992). 20. D. W. Stephan, T. T. Nadasdi, Coord. Chem. Rev.,147, 147 (1996).
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.7 From Metal Atom and Related Reactions 3.8.3.7.1 Abstraction Processes
115
21. R. Steudel, M. Kustos, V. Munchow, U. Westphal, Chem. Ber., Recueil, 130, 575 (1997). 22. A. A. Pasynskii, I. L. Eremenko, Yu. V. Rakitin, V. M. Novotortsev, V. T. Kalinnikov, G. G. Aleksandrov, Yu. T. Struchkov, J . Organomet. Chem., 165, 57 (1979). 23. N. Ueyama, T. Okamura, A. Nakamura, J . Am. Chem. Soc., 114, 8129 (1992). 24. B. E. Schultz, S. F. Gheller, M. C. Muetterties, M. J. Scott, R. H. Holm, J . Am. Chem. Soc., 115, 2714 (1993). 25. T. Shibahara, H. Akashi, Inorg. Synth., 29, 254 (1992). 26. T. E. Burrow, D. L. Hughes, A. J. Lough, M. J. Maguire, R. H. Morris, R. L. Richards, J . Chem. SOC.,Dalton Trans., 2583 (1995). 27. P. M. Boorman, B. D. O’Dell, J . Chem. Soc., Dalton Trans., 257 (1980). 28. H. Kawaguchi, K. Tatsumi, J . Am. Chem. SOC.,117, 3885 (1995). 29. W. S. Bigham, P. A. Shapley, Inorg. Chem., 30, 4093 (1991). 30. C. E. Forde, A. J. Lough, R. H. Morris, R. Ramachandran, Inorg. Chem., 35, 2747 (1996). 31. T. B. Rauchfuss, T. D. Weatherill, Inorg. Chem., 21, 827 (1982). 32. S. C. Tang, S. Koch, G. C. Papaefthymiou, S. Foner, R. B. Frankel, J. A. Ibers, R. H. Holm, J . Am. Chem. Soc., 98, 2414 (1976). 33. C. G. Kuehn, H. Taube, J . Am. Chem. Soc., 98, 689 (1976). 34. M. Nishio, H. Matsuzaka, Y. Mizobe, M. Hidai, Organometallics, 15, 965 (1996). 35. D. de Montauzon, R. Poilblanc, Inorg. Synth., 20,237 (1980). 36. P. Kalck, P.-M. Pfister, T. G. Southern, A. Thorez, Inorg. Synth., 23, 123 (1985). 37. T. Gaines, D. M. Roundhill, Inorg. Chem., 23, 2521 (1974). 38. R. Hahn, A. Nakamura, K. Tanaka, Y. Nakayama, Inorg. Chem., 34, 6562 (1995). 39. T. B. Rauchfuss, D. M. Roundhill, J . Am. Chem. Soc., 97, 3386 (1975). 40. M. Howe-Grant, S. Lippard, Inorg. Synth., 20, 101 (1980). 41. J. R. Dilworth, J. Hu, Adt.. Inorg. Chem., 40, 411 (1994). 42. P. R. Stafford, T. B. Rauchfuss, A. K. Verma, S. R. Wilson, J . Organometal. Chem., 526, 203 (1996). 43. K. Schwochau, Angew. Chem., Int. Ed. Engl. 33,2258 (1994). 44. D. Collison, C. D. Garner, J. A. Joule, Chem. SOC.Rev., 25, 25 (1996). 45. D. Sellmann, B. Hadawi, F. Knoch, Inorg. Chim. Acta., 244, 213 (1996). 46. F. Osterloh, W. Saak, S. Pohl, J . Am. Chem. SOC., 119, 5648 (1997).
3.8.3.7From Metal Atom and Related Reactions 3.8.3.7.1 Abstraction Processes
Chromium atoms desulfurize thiophene and PhzS to form Cr-S solids. Similarly, Ni atoms codeposited with CS2 efficiently yield NiS and a (CS), Molybdenum atoms abstract S from organic molecules cleanly4; a comparison was made between Mo and C atom reactions: Mo
-cs With Mo atoms, the ratio of cyclopropane to propene was 1 : 12, whereas for C atoms it was 10: 14,5. (K. J. KLABUNDE)
1. 2. 3. 4. 5.
T. Chivers, P. L. Timms, J . Organomet. Chem., 118, C37 (1976). S. Togashi, J. G. Fulcher, B. R. Cho, M. Hasegawa, J. A. Gladysz, J . Org. Chem., 45,3044 (1980). K. J. Klabunde, unpublished results. A. H. Reid, P. B. Shevlin; T. R. Webb, S. S. Yun, J . Org. Chem., 49, 4728 (1984). P. S. Skell, K. J. Klabunde, J. H. Plonka, J. S. Roberts, D. L. Williams-Smith, J . Am. Chem. Soc., 95, 1547 (1973).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.8.3 Formation of the Sulfur-Transition and Inner-Transition Metal Bond 3.8.3.7 From Metal Atom and Related Reactions 3.8.3.7.1 Abstraction Processes
115
21. R. Steudel, M. Kustos, V. Munchow, U. Westphal, Chem. Ber., Recueil, 130, 575 (1997). 22. A. A. Pasynskii, I. L. Eremenko, Yu. V. Rakitin, V. M. Novotortsev, V. T. Kalinnikov, G. G. Aleksandrov, Yu. T. Struchkov, J . Organomet. Chem., 165, 57 (1979). 23. N. Ueyama, T. Okamura, A. Nakamura, J . Am. Chem. Soc., 114, 8129 (1992). 24. B. E. Schultz, S. F. Gheller, M. C. Muetterties, M. J. Scott, R. H. Holm, J . Am. Chem. Soc., 115, 2714 (1993). 25. T. Shibahara, H. Akashi, Inorg. Synth., 29, 254 (1992). 26. T. E. Burrow, D. L. Hughes, A. J. Lough, M. J. Maguire, R. H. Morris, R. L. Richards, J . Chem. SOC.,Dalton Trans., 2583 (1995). 27. P. M. Boorman, B. D. O’Dell, J . Chem. Soc., Dalton Trans., 257 (1980). 28. H. Kawaguchi, K. Tatsumi, J . Am. Chem. SOC.,117, 3885 (1995). 29. W. S. Bigham, P. A. Shapley, Inorg. Chem., 30, 4093 (1991). 30. C. E. Forde, A. J. Lough, R. H. Morris, R. Ramachandran, Inorg. Chem., 35, 2747 (1996). 31. T. B. Rauchfuss, T. D. Weatherill, Inorg. Chem., 21, 827 (1982). 32. S. C. Tang, S. Koch, G. C. Papaefthymiou, S. Foner, R. B. Frankel, J. A. Ibers, R. H. Holm, J . Am. Chem. Soc., 98, 2414 (1976). 33. C. G. Kuehn, H. Taube, J . Am. Chem. Soc., 98, 689 (1976). 34. M. Nishio, H. Matsuzaka, Y. Mizobe, M. Hidai, Organometallics, 15, 965 (1996). 35. D. de Montauzon, R. Poilblanc, Inorg. Synth., 20,237 (1980). 36. P. Kalck, P.-M. Pfister, T. G. Southern, A. Thorez, Inorg. Synth., 23, 123 (1985). 37. T. Gaines, D. M. Roundhill, Inorg. Chem., 23, 2521 (1974). 38. R. Hahn, A. Nakamura, K. Tanaka, Y. Nakayama, Inorg. Chem., 34, 6562 (1995). 39. T. B. Rauchfuss, D. M. Roundhill, J . Am. Chem. Soc., 97, 3386 (1975). 40. M. Howe-Grant, S. Lippard, Inorg. Synth., 20, 101 (1980). 41. J. R. Dilworth, J. Hu, Adt.. Inorg. Chem., 40, 411 (1994). 42. P. R. Stafford, T. B. Rauchfuss, A. K. Verma, S. R. Wilson, J . Organometal. Chem., 526, 203 (1996). 43. K. Schwochau, Angew. Chem., Int. Ed. Engl. 33,2258 (1994). 44. D. Collison, C. D. Garner, J. A. Joule, Chem. SOC.Rev., 25, 25 (1996). 45. D. Sellmann, B. Hadawi, F. Knoch, Inorg. Chim. Acta., 244, 213 (1996). 46. F. Osterloh, W. Saak, S. Pohl, J . Am. Chem. SOC., 119, 5648 (1997).
3.8.3.7From Metal Atom and Related Reactions 3.8.3.7.1 Abstraction Processes
Chromium atoms desulfurize thiophene and PhzS to form Cr-S solids. Similarly, Ni atoms codeposited with CS2 efficiently yield NiS and a (CS), Molybdenum atoms abstract S from organic molecules cleanly4; a comparison was made between Mo and C atom reactions: Mo
-cs With Mo atoms, the ratio of cyclopropane to propene was 1 : 12, whereas for C atoms it was 10: 14,5. (K. J. KLABUNDE)
1. 2. 3. 4. 5.
T. Chivers, P. L. Timms, J . Organomet. Chem., 118, C37 (1976). S. Togashi, J. G. Fulcher, B. R. Cho, M. Hasegawa, J. A. Gladysz, J . Org. Chem., 45,3044 (1980). K. J. Klabunde, unpublished results. A. H. Reid, P. B. Shevlin; T. R. Webb, S. S. Yun, J . Org. Chem., 49, 4728 (1984). P. S. Skell, K. J. Klabunde, J. H. Plonka, J. S. Roberts, D. L. Williams-Smith, J . Am. Chem. Soc., 95, 1547 (1973).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
1 1 6 3.8 Formation of Bonds between the Group VIB Elements
3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
3.8.3.7.2 Oxidative Addition/Complexation Reactions
Oxidative addition of C6F5Br to Pd atoms yields C5F5-Pd-Brspecies that are highly reactive toward many ligands, including sulfides' (Table 1): TABLE1. PALLADIUM-SULFIDE COMPLEXES PREPARED USINGMETALATOMS Complex
Yield (%)a
~~
Ref.
~
C6F,-Pd-Br [S(Ph),], C6F,-Pd-Br [S(Et),12 C6F,-Pd-Br [S(Me),l2
10 4 3
~~
"Based on metal vaporized.
S(W2 C6FsBr
+ Pd-
CsFs-Pd-Br-
(MeM
I
C6F5-Pd-Br
(a)
I
S(W2 The intermediate is isolable as a polymeric solid that can be dissolved in acetone followed by addition of the sulfide. The resulting product is purified by chromatographic separation on Fluorosil'. Codeposition of toluene and Ni atoms yields the reactive z-arene complex bearing toluene-solvated Ni atoms, which reacts vigorously with a CS2/P(Ph)3mixture to yield a CS2 complex2:
(K. J. KLABUNDE)
1. K. J. Klabunde, B. B. Anderson, K. Neuenschwander, Inorg. Chem., 19, 3719 (1980). 2. R. G. Gastinger, K. J. Klabunde, Transition Met. Chem., 4, l(1979).
3.8.4 Formation of the Selenium-, Tellurium-, and Polonium-Transition and Inner Transition Metal Bond Transition metal chalcogenides are synthesized in various ways1B2:(1) from direct reaction of the elements, ( 2 ) by molten salt reaction, (3) from reaction of chalcogen with metal compounds, (4) via polychalcogenide reaction with metal compounds, (5) from pressurized solventothermal reactions, (6) and by using other reactive chalcogen compounds and ions. Typically the chemistry of the selenides, tellurides, and so far as known, the polonides is similar to that of sulfide. However, combination of the elements at elevated temperatures (400-1000°C) often yields nonstoichiometric compounds that can be
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
1 1 6 3.8 Formation of Bonds between the Group VIB Elements
3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
3.8.3.7.2 Oxidative Addition/Complexation Reactions
Oxidative addition of C6F5Br to Pd atoms yields C5F5-Pd-Brspecies that are highly reactive toward many ligands, including sulfides' (Table 1): TABLE1. PALLADIUM-SULFIDE COMPLEXES PREPARED USINGMETALATOMS Complex
Yield (%)a
~~
Ref.
~
C6F,-Pd-Br [S(Ph),], C6F,-Pd-Br [S(Et),12 C6F,-Pd-Br [S(Me),l2
10 4 3
~~
"Based on metal vaporized.
S(W2 C6FsBr
+ Pd-
CsFs-Pd-Br-
(MeM
I
C6F5-Pd-Br
(a)
I
S(W2 The intermediate is isolable as a polymeric solid that can be dissolved in acetone followed by addition of the sulfide. The resulting product is purified by chromatographic separation on Fluorosil'. Codeposition of toluene and Ni atoms yields the reactive z-arene complex bearing toluene-solvated Ni atoms, which reacts vigorously with a CS2/P(Ph)3mixture to yield a CS2 complex2:
(K. J. KLABUNDE)
1. K. J. Klabunde, B. B. Anderson, K. Neuenschwander, Inorg. Chem., 19, 3719 (1980). 2. R. G. Gastinger, K. J. Klabunde, Transition Met. Chem., 4, l(1979).
3.8.4 Formation of the Selenium-, Tellurium-, and Polonium-Transition and Inner Transition Metal Bond Transition metal chalcogenides are synthesized in various ways1B2:(1) from direct reaction of the elements, ( 2 ) by molten salt reaction, (3) from reaction of chalcogen with metal compounds, (4) via polychalcogenide reaction with metal compounds, (5) from pressurized solventothermal reactions, (6) and by using other reactive chalcogen compounds and ions. Typically the chemistry of the selenides, tellurides, and so far as known, the polonides is similar to that of sulfide. However, combination of the elements at elevated temperatures (400-1000°C) often yields nonstoichiometric compounds that can be
117 3.8 Formation of Bonds between the Group VIB Elements 3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
considered alloys3. Because of similar electronegativity differences between the heavier chalcogenides and the transition metals, these are abundant and will be discussed in Section 3.11. Homoleptic complexes have been formed via a molten salt reaction. This is a particularly good method for making early transition metal andf-block chalcogenides, which often tend to pull oxygen from solvent molecules. A prereaction of K and Te at 650°C followed by the subsequent addition of Te and M and heating to 900°C forms K4M3TeI7 (M = Zr, Hf)4. Reactions of K2Se, elemental Se, and Nb at 375°C for 100 h produce K6[Nb4Se4(Se2)9]5.The KFeS26,K4[U(Se2)4]7,and K[Ce(Se2)z]8were synthesized by essentially the same method. Heavy elemental chalcogens react less commonly than sulfur analogues. Nonetheless, low oxidation state metals are oxidized by Se, whereas Te lacks the oxidizing ability. Either gray or red selenium can convert [MSe4I2- to [MS(Se4)12- (M = Mo or W)93'0. At elevated temperature, (y5-Cp),MMe2 reacts with Se yielding the insertion product ($-Cp),M(SeMe); l l . In organometallic compounds, when [ y ' - C p M 0 ( C 0 ) ~ 1reacts ~ with SeZ-, [~'-CpMo(Se2)(CO),]- forms, which in turn yields [q'-CpM~(Se,)~l-upon reaction with elemental Se converting Mo2+ to Mo4+12,13. Similarly, [ $ - C P C ~ ( C O ) ~ ] ~ reacts with Se forming [~'-Cp2Cr2(Se2)(CO)4]. A polychalcogenide synthesis can also be used to form [$-CpMo(Se4),]- by reacting [ ~ ' - C P M O ( C O )with ~ ] ~ Na and Se in D M F at 60"C'4. Isoelectronic Mn species form with similar reactant^'^. Elemental Te and ReCl, in a 2 : 1 ratio yield ResTe6C16(TeC12)216"7,whereas these substances combine with [Fe(C0),I2- forming [Fe2(Te2)2(Co)6]2-'s.Cobalt and Rh complexes of type y5-Cp2*M2(Se)(Se4) can be made from the carbonyl Phosphine complexes [ { C P R ~ ( P ~ ~ P ) ~+,) Z SC~( PZ~I ~ P ) Z R ~ ( C O ) Z+,( S ~CZ( t)rIi p h o s ) ~ R h ~ ( S e+,~ ) ~ I ~ [(dppe),Ir(Se,),] +,and [(dmpe)21r(Se4)2]+ are made by oxidizing the phosphine complex with Se22-26.A polarizing organic solvent, N-methylimidazole, dissolves metals and the chalcogen and assists the oxidation as demonstrated by27: Fe(CO)5
+ Se-
N-MeIm
[Fe(N-MeIm),J [Fe(Se4)2(CO)z]
(a)
The analogue [ R U ( S ~ ~ ) ~ ( C Ois) ~synthesized ]~using the polyselenide Na2Se5 with Ru3(CO),2 2 8 . The most common method for forming the M-E bond is by using a polychalcogenide reagent. Some common reagents are Li,Se2, Na2Se2,K2Se3,Li2Se5,Na2Se5,K2Se5, (Me4N)2Se5,LizSe6,(Me4N)2Se6,NazTe2,K2Te2, Ph2Te2,K2Te4, and (Ph4P)2Te429. These polychalcogenides are sometimes generated in sku3' as follows:
The product in reaction (b) can be obtained via reaction of Li2Se6 and FeCp(C0)I in D M F at 100"C31.Combination of Se and K2Se generates [Se4I2-, which in turn is combined with [IrCl(cyclooctene)z]2 yielding [1r(Se4),l3- 32. NbC15 reacts with K2Te4yielding a capped trigonal prism of Te atoms around the MC15 (M = Mo, W) reacts with K2E2(E = Se, Te) forming Nb cation [NbTelo13- (l)33. [ME'(E4)J- (2) where E' may be 0, since this position is susceptible to O2 a t t a ~ k ~ , ~ ~ .
1 1 8 3.8 Formation of Bonds between the Group VIB Elements 3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition Te
M
(The hatched wedges clarify the trigonal prism)
I
(M = Mo, W)
2
1
CrC1, and CoC12 react similarly with polychalcogenides forming cluster compounds of the [M3(E4)6]3Polyselenides react with MnC12 or Mn2(CO)lo yielding [Mn(Se4)2]2-36-38,Pt'" is stabilized by polyselenide as3': Pt(xanthate)2
+ Li2Se5+ Ph4PC1-
DMF
[Ph,P],[Pt(Se,),]
DMF
(4
Group IVB to Se bonds exist in organometallic compounds of type $-Cp2M(Se5), made by reaction of q5-Cp,MC12 with Se:-40-42. An interesting derivative of this is made by abstracting, with a phosphine, an Se atom from ($-RCp),TiSe5 to form {(q5-RCp),Ti}2(p2-Se2)243. This product is also obtained by reaction of ($-RCp),TiC12 with Li2Se2:
y5-MeCp To date, no Te analogues exist. When q5-CpMC12(M = Mo, W) reacts with Na2Se5, q5-CpM(Se4)results (2)44.(q5-Cp),MC12(M = Ti, Zr, V, Nb, Mo, W) reacts with [PhEIand related anions yielding (q5-Cp)M(EPh)245-46. If the starting materials are equimolar amounts of M(CO)6 (M = Cr, Mo, W) and Te:- in DMF, [M(Te4)(CO),l2- forms4'. However, this reaction is highly dependent on reactant stoichiometry, length of Te:-, and temperature; e.g., if the reaction is heated to 100°C in DMF, the cluster [M6(Te2)4(CO)1sl2-(3) forms instead48.Excess Cr(CO), yields [Cr4(Te2)(C0)2n]2-49. The analogous Mn or Re also is sensitive, since [M2(Sez)2(C0)6]2- or [M2(Se4)2(C0)6]2- is the likely product at RT, depending on the amount of Se ~ s e d ~ 'But ,~~ if .100°C is used, [Mn(Se4)J2- is formed, which incidentally can also be obtained by heating [M2(Se4)2(C0),]2- to 90"C3*. A good leaving group on Fe [i.e., (C4H,)Fe(CO),] can be used with Te:- to form [Fez(Te)(Te2)(C0)6]2-5'.Somewhat surprisingly, an RT reaction of Fe(CO)5/KOH/MeOH and T e 0 2 yields [Te{Fe(CO)4}3]2-52.A good leaving group on Co also seems to help form Co-Se bonds, as evidenced by (triphos)Co(NCS), reacting with Se:- to yield (triphos)
3.8 Formation of Bonds between the Group VIB Elements 119 3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition Co(Se4)j3.Last, relatively large clusters [NiNi9Te3(C0)1j] 2 - and [Ni8Te4(C0)12]2form from reaction of [Ni6(C0)6]2- with Ph2Te254s55, while Pt(SePh)2(PPh3)2is generated from Pt(PPh3)4 and Ph2Se256.
Te
\\
Te-
Te
3
(The carbonyls are omitted for clarity) 4
The hydrothermal or solventothermal method usually requires a species that will aid in crystallization. The group IA polychalcogenides serve as both reactant and cation source for the reactions. The solvent is typically H 2 0 ,although other polar solvents (e.g., alcohols, amines, DMF, THF, MeCN) will dissolve quaternary ammonium or phosphonium polychal~ogenides~~. Vanadium and K2Se4 react in MeOH at 135°C forming K4[V202Se2(Se4)2)2MeOH and K4 [V202Se2(Se2)(Se4)] 0.65MeOH depending on the reaction time58.A large cluster, K12[ M O ~ ~ S ~ , ( S ~ ~ ) forms ~ , ( Supon ~ ~ ) reacting ~], Mo, K2Se4, and H 2 0 (1 : 4 : 33 equiv) at 140°C for 60 h59.When the equivalent ratio is changed to 1 : 1.5 : 222, the K2 [ M O ~ S ~ ( S ~ , ) , ( S ~ , )cluster ( S ~ ~forms6'. )~] When M o o 3 is used and the K2Se4equivalents are increased to 2, Ks[Mo9(Se)4(Se2)ls]. 4 H 2 0 forms6'. Increasing reaction time yields K6[ M ~ ~ ( S e ) , ( s e ~6) H , ~2]0 ; ultimately, after 30 days, K2[ M ~ ~ ( s e ) ( S e , ) forms. , ] ~ ~ Large clusters containing Fe-Te bonds seem to be in order when a D M F solution of Fe(CO), is heated to 85°C with (PPh4)2Te4 to yield [FesTe8(Te2)(CO)20]2-(4)49. The same product was also isolated using a hydrothermal method whereby Fe(CO)j, Na2Te2, Ph4PC1, and H 2 0 are heated to l10'C62. The importance of the counterion is indicated by the reaction of K2PtCI4 or PdC12, K2Se4, KOH, and H 2 0 for 24 h at 110°C yielding K4Pt4SeZz6,or K2 [PdSelo]64 (a combination of [Pd(Se4)J2 - and Pd(Se&12 -). The small counterion (K') yields the polymeric K2[PdSelo], whereas the large counterion (Ph4P+)shields [Pd(Se4),12- anions from each other, not allowing the Se atoms to come into close contact. Organometallic compounds also undergo solventothermal reactions as evidenced by reaction of Fe(CO)5and Na2Se2heated in MeOH to yield [Fe4Se2(Se2)(CO),2]2-62. Large clusters65are in order here, however, since R U ~ ( C Oreacts ) ~ ~ with Na2Te2in the presence of Ph4PCI and H 2 0 at 110°C forming (Ph4P)2[Ru6(Te2)7(C0)12]62. Not surprisingly, many of the M-E bonds form from reaction of A2E (A = alkali metal) with transition metal compounds. These are generated by reaction of LiBEt3H with the element66.Reaction of FeC1, with Li2Se and Na[PhNC(O)Me] in EtOH yields the cluster [NagFe2&38]g- 6 7 . The anions [Fe2E2(NO),12- (E = chalcogen) form when Fe212(N0)4reacts with Se2- or Te2-, or they can be alkylated to give neutral products, Fez(ER),(NO),. Alternatively, Fe,I,(NO), reacts directly with [PhE] - to give (pEPh)2 dimers6'. The cluster compound Fe,Te2(C0)9 forms in good yield by treatment of Fe12(C0)4 with Li2Te69,although it is easily prepared from [HFe(CO)J and TeOi- ". [HFe(CO),]- will also react with [SSe,12- to give sublimable a
120 3.8 Formation of Bonds between the Group VIB Elements
3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
Fez(Se2)(C0),56. NaSeH reacts with NiClz in the presence of dppe yielding [Ni3Se2(dppe)3]2C71,while NaHTe reacts with [Fe(TePhL]’- yielding the cubane structure [Fe4(p3-Te)4(TePh)4]3-72. Polysulfides are often synthesized using H2S, Ss, and a base. H2E (E = Se or Te) is much more difficult to work with because of the toxicity and low stability of these chalcogens. Yet a number of syntheses have employed H2Se as a reactant. ($-Cp)2TiC12 upon addition of NEt3 [($-Cp)4Ti&6]74 is reacts forming [{(q5-Cp)2Ti}2(Se2)]2(Se)73; formed. However, other compounds containing these heavy chalcogens have been used to synthesize transition metal-chalcogen bonds. A less volatile, and therefore less toxic, reagent is HSePh. In the presence of NEt3, (q5-Cp),ZrC12yields ( ~ ~ - C p ) , Z r ( S e p h Likewise, ) , ~ ~ . (Me3Si)2Seis less volatile, and when allowed to react with y5-CpTiC13in THF, it yields [y5-Cp4Ti4(p4-0)(p2-Se)(p3-Se)2(p3Se2)2]76.Similarly, with ( V ~ - M ~ C ~ )it~yields V C ~[~5-(MeCp)zV2(p2-Se)(p2-Se2)(p2-~2~, Sez)l7’. This product also forms from reaction with H2Se7’:
-
Se
(qs-MeCp)2VC12t (Me&Se (q5-MeCp)2VCI2+ H2Se
qs-MeCp
(q5-MeCp)2V(Se5)
(4 Se-Se
A homoleptic V-Se compound forms using a similar, yet even less volatile
(dimethyloctylsilyl)zSe, with N H 4 N 0 3 in the presence of Et4NCl/NEt3 forming (Et4N2 Group VIA-Se bonds are made by reacting [MSe4lZ- (M = Mo or W) with (NC5Hlo)2Se2forming [MoO(Se4),12- or by reacting SeS2 with [WSe4I2- yielding [WS(Se),]’-, both of which take structures 280.Several MSeX, (M = Nb, Ta, Mo, W; X = C1, F; n = 2, 3,4) are prepared from reaction of metal halide and Sb2Se381.82. H2Te, is generated in situ via AI2Te3 and HCI. When this mixture reacts with SII{W(CO)~}~, W3(Te2)(C0)15forms (5)”. This mixture also forms (~5-Cp*)2Rez(Te2)2(CO)4 from
(WSW
‘Te=Te
1
W(C0)S 5
‘w(co)s
(y5-Cp*)Re(C0),(THF) under UV lights4. The analogous Mn product forms using COSe from the same Mn starting materials5. Chelates can be prepared from CSSe and related heterocumuleness6. Se
3.8 Formation of Bonds between the Group VIB Elements 3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
121
Selenium metal with CC14 forms CSez at high temperature, which in turn can be used to make diselenocarbamates that form large numbers of transition metal comp l e x e ~The ~ ~incorporation ~ ~ ~ . of Te has benefited from the reactivity of Et3PTe.Interestingly, Te substitutes for Se in several complexes by reacting Et3PTe with, e.g., Refluxing a toluene solution of [Ni(Se4)I2-, yielding [Ni4Te4(Te2)2(Te3),]4-Sg. Mn2(CO)lowith Et3PTe yields (Et3P)4Mn2(Te2)(C0)6go. The same reaction conditions were used in reacting ( $ - C P ) ~ F ~ ~ ( C Oto) ,yield (Et3P)z(y5-Cp)zFez(Te2)(CO)z. Pyrolysis at 275°C yields FeTegl. One of the oldest syntheses of a M-Se bond is the reaction of Se0:- ion with [Fe(CO)4]2- to yield Fe2(Sez)(C0)6 (6)". The analogous
6 Fe2(Te2)(CO),was made in the same reaction vessel as Fe3(Te)z(C0)993. Although there are many reactions with polychalcogenides as seen above, few reactions use polychalcogen cation^^^,^^:
+ W(CO),- [W(C0)4(cyclo-Te3)]2t Se?" + W(CO)6 + Fe(C0)5[WFe(CO)S(Sez)]2' Te?'
(h)
(4 (P. F. BRANDT)
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19.
L. C. Roof, J. W. Kolis, Chem. Reo., 93, 1037, (1993). A review. M. G. Kanatzidis, S.-P. Huang, Coord. Chem. Reo., 130, 509 (1994). N. N. Greenwood, A. Earnshaw, Chemistry ofthe Elements, Pergamon Press, New York, 1984. P. M. Keane, Y.-J. Lu, J. A. Ibers, in Inorganic Synthesis, Vol. 30, D. W. Murphy, L. V. Interrante, eds., Wiley, New York, 1995, p. 86. S. Schreiner, L. E. Aleandre, D. Kang, J. A. Ibers, Znorg. Chem., 28, 392 (1989). Y. Park, T. J. McCarthy, A. C. Sutorik, M. G. Kanatzidis, in Inorganic Synthesis, Vol. 30, D. W. Murphy, L. V. Interrante, eds., Wiley, New York, 1995, p. 88. A. C. Sutorik, M. G. Kanatzidis, J . Am. Chem. Soc., 113, 7754 (1991). A. C. Sutorik, M. G. Kanatzidis, Angew. Chem., Int. Ed. Engl., 31, 1594 (1992). R. W. M. Wardle, S. Bhaduri, C.-N. Chau, J. A. Ibers, Inorg. Chem., 27, 1747 (1988). A. Muller, E. Urichemeyer, H. Bogge, M. Penk, D. Rehder, Chimia, 40, 50 (1986). B. Gautheron, G. Tainturier, P. Meunier, J . Organomet. Chem., 209, C49 (1981). J. Adel, F. Weller, K. Dehnicke, J . Organomet. Chem., 347, 343 (1988). L. Y. Goh, C. Wei, E. Sinn, J . Chem. Soc., Chem. Commun., 462 (1985). R. M. H. Banda, J. Cusick, M. L. Scudder, D. C. Craig, I. G. Dance, Polyhedron, 8,1999 (1989). M. Herberhold, D. Reiner, U. Thewalt, Angew. Chem., Int. Ed. Engl., 22, 1000 (1983). Y. V. Mironov, M. A. Pell, J. A. Ibers, Inorg. Chem., 35, 2709 (1996). Y. V. Mironov, M. A. Pell, J. A. Ibers, Angew. Chem., Int. Ed. Engl., 35, 2854 (1996). R. E. Bachman, K. H. Whitmire, Organometallics, 12, 1988 (1993). H. Brunner, W. Meier, B. Nuber, J. Wachter, M. L. Ziegler, Angew. Chem., Int. Ed. Engl., 25,907 (1986).
122 3.8 Formation of Bonds between the Group VIB Elements
3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
20. H. Brunner, N. Janietz, W. Meier, J. Wachter, E. Herdtweck, W. A. Herrmann, 0. Serhadli, M. L. Ziegler, J . Organomet. Chem., 347, 237 (1988). 21. W. A. Herrmann, J. Rohrmann, Chem. Ber., 119, 1437 (1986). 22. J. Amarasekera, E. J. Houser, T. B. Rauchfuss, C. L. Stern, Inorg. Chem., 31, 1614 (1992). 23. D. H. Farrar, K. R. Grundy, N. C. Payne, W. R. Roper, A. Walker, J . Am. Chem. Soc., 101,6577 (1979). 24. C. Bianchini, C. Mealli, A. Meli, M. Sabat, J . Am. Chem. Soc., 107, 5317 (1985). 25. A. P. Ginsberg, W. E. Lindsell, C. R. Sprinkle, K. W. West, R. L. Cohen, Inorg. Chem., 21, 3666 (1982). 26. A. P. Ginsberg, J. H. Osborne, C. R. Sprinkle, Inorg. Chem., 22, 1781 (1983). 27. T. B. Rauchfuss, S. Dev, S. R. Wilson, Inorg. Chem., 31, 153 (1992). 28. M. Draganjac, S. Dhingra, S.-P. Huang, M. G. Kanatzidis, Inorg. Chem., 29, 590 (1990). 29. M. G. Kanatzidis, Angew. Chem., Int. Ed. Engl., 34, 2109 (1995); and references therein. 30. H. Strasdiet, B. Krebs, G. Henkel, Inorg. Chim. Acta, 89, L11 (1984). 31. A. Miiller, M.-L. Ha-Eierdanz, G. Krauter, K. Dehnicke, Z . Naturforsch., Teil B, 46, 175 (1991). 32. T. E. Albrecht-Schmitt, J. A. Ibers, Inorg. Chem., 35, 7273 (1996). 33. W. A. Flomer, J. W. Kolis, J . Am. Chem. Soc., 110, 3682 (1988). 34. W. A. Flomer, J. W. Kolis, Inorg. Chem., 28, 2513 (1989). 35. W. A. Flomer, S. C. ONeal, W. T. Pennington, D. Jeter, A. W. Cordes, J. W. Kolis, Angew. Chem., Int. Ed. Engl., 27, 1702 (1988). 36. G. Krauter, M.-L. Ha-Eierdanz, A. Miiller, K. Dehnicke, Z . Naturforsch., Teil B, 45, 695 (1990). 37. M. A. Ansari, C. H. Mahler, G. S. Chorghade, Y.-J. Lu, J. A. Ibers, Inorg. Chem., 29,3832 (1990). 38. S. C. O’Neal, W. T. Pennington, J. W. Kolis, Inorg. Chem., 29, 3134 (1990). 39. M. A. Ansari, J. A. Ibers, Inorg. Chem., 28, 4068 (1989). 40. H. Kopf, B. Block, M. Schmidt, Chem. Ber., 101, 272 (1968). 41. D. Fenske, J. Adel, K. Dehnicke, Z . Naturforsch., Teil B, 42, 931 (1987). 42. N. Albrecht, E. Weiss, J . Organomet. Chem., 355, 89 (1988). 43. D. M. Giolando, M. Papavassiliou, J. Pickardt, T. B. Rauchfuss, R. Steudel, Inorg. Chem., 27, 2596 (1988). 44. H. Kopf, W. Kahl, A. Wirl, Angew. Chem., Int. Ed. Engl., 9, 801 (1970). 45. M. Sato, T.Yoshida, J . Organomet. Chem., 94, 401 (1975). 46. M. Sato, T.Yoshida, J . Organornet. Chem., 87, 217 (1975). 47. W. A. Flomer, S. C. O’Neal, J. W. Kolis, D. Jeter, A. W. Cordes, Inorg. Chem., 27, 969 (1988). 48. L. C. Roof, W. T. Pennington, J. W. Kolis, J . Am. Chem. Soc., 112, 8172 (1990). 49 L. C. Roof, W. T. Pennington, J. W. Kolis, Angew. Chem., Int. Ed. Engl., 31, 913 (1992). 50 S. C. ONeal, W. T. Pennington, J. W. Kolis, Can. J . Chem., 67, 1980 (1989). 51 B. W. Eichhorn. R. C. Haushalter. J. S. Merola. Inora. Chem.. 29. 728 (1990). , , C? JL: R. E. Bachman,’K. H. Whitmire, inorg. Chem., 33, 2527 (1994). 53. M. Schmidt, R. Holler, Rec. Chim.Miner., 20, 763 (1983). 54. A. J. Kahaian, J. B. Thoden, L. F. Dahl, J . Chem. Soc., Chem. Commun., 353 (1992). 55. I. Dance, K. Fisher, in Progress in Inorganic Chemistry, Vol. 41, K. D. Karlin, ed., Wiley, New York, 1994, p. 637. A review. 56. V. W. Day, D. A. Lesch, T. B. Rauchfuss, J . Am. Chem. Soc., 104, 1290 (1982). 57. W. S. Sheldrick, M. Wachhold, Angew. Chem., Int. Ed. Engl., 36, 206 (1997); A review. 58. J.-H. Liao, L. Hill, M. G. Kanatzidis, Inorg. Chem., 32, 4650 (1993). 59. J.-H. Liao, M. G. Kanatzidis, J . Am. Chem. Soc., 112, 7400 (1990). 60. J.-H. Liao, M. G. Kanatzidis, Inorg. Chem., 31, 431 (1992). 61. J.-H. Liao, J. Li, M. G. Kanatzidis, Inorg. Chem., 34, 2658 (1995). 62. S.-P. Huang, M. G. Kanatzidis, Inorg. Chem., 32, 821 (1993). 63. K.-W. Kim, M. G. Kanatzidis, Inorg. Chem., 32, 4161 (1993). 64. K.-W. Kim, M. G. Kanatzidis, J . Am. Chem. Soc., 114, 4878 (1992). 65. R. L. Holliday, L. C. Roof, B. Hargus, D. M. Smith, P. T. Wood, W. T. Pennington, J. W. Kolis, Inorg. Chem., 34, 4392 (1995). 66. J. A. Gladysz, V. K. Wong, B. S. Jick, J . Chem. Soc., Chem. Commun.,838 (1978). 67. J.-F. You, R. H. Holm, Inorg. Chem., 30, 1431 (1991). 68. T. B. Rauchfuss, T. D. Weatherill, Inorg. Chem., 21, 827 (1982). 69. H. Schumann, M. Magerstadt, J. Pickardt, J . Organornet. Chem., 240, 407 (1982).
3.8 Formation of Bonds between the Group VIB Elements 3.8.4 Formation of the Se-, Te-, and Po-Transition and Inner Transition
123
70. P. F. Brandt, D. A. Lesch, P. R. Stafford, T. B. Rauchfuss, in Inorganic Synthesis, A. H. Cowley, ed., Vol. 31, Wiley, New York, 1997, p. 112. 71. K. Matsumoto, N. Saiga, S. Tanaka, S. Ooi, J . Chem. Soc., Dalton Trans., 1265 (1991). 72. W. Simon, A. Wilk, B. Krebs, G. Henkel, Angew. Chem., Int. Ed. Engl., 26, 1009 (1987). 73. F. Bottomley, T.-T. Chin, G. 0. Egharevba, L. M. Kane, D. A. Pataki, P. S. White, Organometallics, 7, 1214 (1988). 74. F. Bottomley, R. W. Day, Organometallics, 10, 2560 (1991). 75. H. Kopf. J . Organomet. Chem., 14, 353 (1968). 76. P. G. Maue, D. Fenske, Z. Naturforsch., Teil B, 43, 1213 (1988). 77. D. Fenske, J. Ohmer, J. Hachgenei, K. Merzweiler, Angew. Chem., Int. Ed. Engl., 27, 1277 (1988). 78. C. M. Bolinger, T. B. Rauchfuss, A. L. Rheingold, Organometallics, I , 1551 (1982). 79. C.-N. Chau, R. W. M. Wardle, J. A. Ibers, Inorg. Chem., 26, 2740 (1987). 80. R. W. M. Wardle, C. H. Mahler, C.-N. Chau, J.-A. Ibers, Inorg. Chem., 27, 2790 (1988). 81. D. Britnell, G. W. A. Fowles, D. A. Rice, J . Chem. Soc., Dalton Trans., 2191 (1974). 82. G. W. A. Fowles, R. J. Hobson, D. A. Rice, K. J. Shanton, J . Chem. Soc., Chem. Commun., 552 (1976). 83. 0. Scheidsteger, G. Huttner, K. Dehnicke, J. Pebler, J . Angew. Chem., Int. Ed. Engl., 24, 428 ( 1985). 84. W. A. Herrmann, C. Hecht, E. Herdtweck, H.-J. Kneuper, Angew. Chem., Int. Ed. Engl., 26, 132 (1987). 85. M. Herberhold, D. Reiner, U. Thewalt, Z . Naturforsch., Teil B, 35, 1281 (1980). 86. H. Werner, Coord. Chem. Rec., 43, 165 (1982). A review. 87. W.-H. Pan, J. P. Fackler, Jr., J . Am. Chem. Soc., 100, 5783 (1978). 88. W.-H. Pan, J. P. Fackler, Jr., H. W. Chen, Inorg. Chem., 20, 856 (1981). 89. J. M. McConnachie, J. C. Bollinger, J. A. Ibers, Inorg. Chem., 32, 3923 (1993). 90. M. L. Steigerwald, C. E. Rice. J . Am. Chem. Soc., 110, 4228 (1988). 91. M. L. Steigerwald, Chem. Muter., I , 52 (1989). 92. W. Hieber, J. Gruber, Z . Anorg. Allg. Chem., 296, 91 (1958). 93. D. A. Lesch, T. B. Rauchfuss, Inorg. Chem., 20, 3583 (1981). 94. R. Faggiani, R. J. Gillespie, C. Campana, J. W. Kolis, J . Chem. Soc., Chem. Commun., 485 (1987). 95. A. Seigneurin, T. Makani, D. J. Jones, J. Roziere, J . Chem. Soc., Dalton Trans., 2111 (1987).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.9 Formation of the Bond Between
Group VIB (0, S, Se, Te, Po) and Group 0 (Noble Gas) Elements
3.9.1 Introduction Bonds involving the larger members of group 0 and the more electronegative members of group VIB are expected to be most stable (see 2.10.1 for background). It is not surprising that the only well-established bonds of this type involve oxygen bonded to xenon or krypton. Little work has been done with radon because of its radioactivity. Nearly all known examples of the oxygen bond are formed by metathetical reactions of xenon and krypton fluorides or oxyfluorides with compounds containing reduced oxygen. One or more Xe-F bonds are cleaved and replaced by Xe-0 bonds'. Low temperatures and inert solvents are typically used, and equipment generally is composed of or coated with perfluorinated polymers. The Xe-0 bond energy is only about 90 kJ/molz, and all xenon oxides and oxyfluorides are thermodynamically unstable to the formation of Oz. Many of the compounds are shock sensitive, and the original literature should be consulted regarding their synthesis and safe handling. (M. L. THOMPSON) 1. For a review of Group 0 chemistry see N. Bartlett, F. 0. Sladky, in Comprehensiue Inorganic Chemistry, Vol. 1, A. F. Trotman-Dickenson, ed., Pergamon Press, Oxford, 1973, pp 213-330. 2. S . R. G u m , J . Am. Chem. Soc., 87, 2290 (1965)
3.9.2 By Reactions of Xenon Fluorides and Oxyfluorides with Oxides and Oxysalts Early work involved reaction of XeF6 with HzO to yield successively oxyfluorides and the trioxide': XeOF, 2HF XeF6 HzO(a)
+ XeOF4 + HzOXeO2FZ+ HzO-
+ XeO2F2 + 2HF X e 0 3 + 2HF
(b)
(4
Reaction is vigorous and can be difficult to control; solid Xe03 produced is a dangerous explosive. Solutions of the trioxide are obtained by saturating a stream of Nz with XeF6 and bubbling it through H2O2.Caution: liquid H 2 0coming in contact with solid XeF, can cause a violent explosion. The H F by-product can be removed by treatment of the solution with CaCO,. Solid Xe03 is prepared by careful evaporation of the solution. Danger: explosive! 124
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.9 Formation of the Bond Between
Group VIB (0, S, Se, Te, Po) and Group 0 (Noble Gas) Elements
3.9.1 Introduction Bonds involving the larger members of group 0 and the more electronegative members of group VIB are expected to be most stable (see 2.10.1 for background). It is not surprising that the only well-established bonds of this type involve oxygen bonded to xenon or krypton. Little work has been done with radon because of its radioactivity. Nearly all known examples of the oxygen bond are formed by metathetical reactions of xenon and krypton fluorides or oxyfluorides with compounds containing reduced oxygen. One or more Xe-F bonds are cleaved and replaced by Xe-0 bonds'. Low temperatures and inert solvents are typically used, and equipment generally is composed of or coated with perfluorinated polymers. The Xe-0 bond energy is only about 90 kJ/molz, and all xenon oxides and oxyfluorides are thermodynamically unstable to the formation of Oz. Many of the compounds are shock sensitive, and the original literature should be consulted regarding their synthesis and safe handling. (M. L. THOMPSON) 1. For a review of Group 0 chemistry see N. Bartlett, F. 0. Sladky, in Comprehensiue Inorganic Chemistry, Vol. 1, A. F. Trotman-Dickenson, ed., Pergamon Press, Oxford, 1973, pp 213-330. 2. S . R. G u m , J . Am. Chem. Soc., 87, 2290 (1965)
3.9.2 By Reactions of Xenon Fluorides and Oxyfluorides with Oxides and Oxysalts Early work involved reaction of XeF6 with HzO to yield successively oxyfluorides and the trioxide': XeOF, 2HF XeF6 HzO(a)
+ XeOF4 + HzOXeO2FZ+ HzO-
+ XeO2F2 + 2HF X e 0 3 + 2HF
(b)
(4
Reaction is vigorous and can be difficult to control; solid Xe03 produced is a dangerous explosive. Solutions of the trioxide are obtained by saturating a stream of Nz with XeF6 and bubbling it through H2O2.Caution: liquid H 2 0coming in contact with solid XeF, can cause a violent explosion. The H F by-product can be removed by treatment of the solution with CaCO,. Solid Xe03 is prepared by careful evaporation of the solution. Danger: explosive! 124
3.9 Bond Between Group VIB and Group 0 Elements 3.9.2 Reactions of XeF, and Oxyfluorides with Oxides and Oxysalts
125
Xenon oxide tetrafluoride is synthesized by reaction Of XeF6 vapor with air containing a stoichiometric quantity of H 2 0 vapor'. The HF formed, and any unreacted &!&, can be removed by complexation with NaF3. A hazardous route to Xe02F2 involves reaction of XeO, with XeOF44:
+
X e 0 3 XeOF42Xe02F, (4 Fractional distillation separates the Xe02F2 from the nonvolatile X e 0 3 and the much more volatile XeOF,. Decomposition of XeO2F2 produces XeF,, which is slightly more volatile. It can also be removed by fractional distillation, though not very efficiently. Both XeOF, and Xe02F2 can be made by adding successive small increments of HzO to solutions of XeF6 in HF at low temperature. The solution is warmed to RT after each H 2 0 addition; the procedure is continued until the stoichiometric amount of H 2 0 is correct for the desired product5. Xenon tetrafluoride reacts vigorously with excess HzO to form XeO,, via disproportionation6.
+ 2Xe + 1.50, + 12HF
3XeF4 + 6H20-Xe03
(ei
The reaction is less violent than the hydrolysis of X&. Unstable oxyfluoride XeOF, is made by direct reaction of stoichiometric amounts of solid XeF4 and ice, which are mixed at -80°C and warmed slowly to - 50°C with continuous removal of HF7,'. Reaction can also be carried out in liquid HF at -63°C'. Hydrolysis of either XeF4 or XeF6 in base results in disproportionation to perxenates, salts of Xe(VIII)6$'0.With XeF6, the approximate stoichiometry is: 2XeF6
+ 1 6 0 H - + 4Na'
-
Na4XeO6
+ Xe + o2+ 12F- + 8 H 2 0
(f)
The N a salt is insoluble in alkaline solution and precipitates as a hydrate. Perxenates can also be formed by disproportionation of X e 0 , in base or, in higher yield, by oxidation of alkaline Xe(V1) solutions with 0 3 ' 0 . The group IA and IIA perxenates are stable salts, however, in aqueous solution they decompose to Xe(V1) and 0,. Rate of decomposition increases with decreasing pH. Perxenates react with concentrated H 2 S 0 4to form XeO,, an explosively unstable gas' Perxenates react with XeF6 yielding unstable gaseous oxyfluoride Xe03F, and other products'2. Xenon oxide tetrafluoride can also form by reaction of XeF6 with a stoichiometric quantity of Si02'3. 2XeF6 + s i o 2-2XeOF4 + SiF4 (g) The SiF, can be distilled away from less volatile XeOF, and XeF6. Excess S i 0 2 leads to formation of Xe03. Nitrates react with XeF6 to form XeOF,. This safe and convenient route involves reaction of XeF6 with a stoichiometric deficiency of NaNO3I4: XeF,
+ NaN0,
-
NaF
+ XeOF4 + F N 0 2
(hi
The two are mixed at - 196°C and warmed to 70°C for 10 h, then the product is collected at -78°C (82% yield) while the more volatile FNO, is condensed in a - 196°C trap. A deficiency of N a N 0 , is necessary to suppress formation of Xe02F4. NaN0,
+ XeOF,-
NaF
+ Xe02F2 + F N 0 2
(4
A similar reaction occurring with CsNO, has disadvantages as a synthetic route to XeO F4 5 .
126 3.9 Bond Between Group VIB and Group 0 Elements 3.9.2 Reactions of XeF, Fluorides and Oxyfluorides with Oxides and Oxysalts
Reaction of N2O5, [N02][N0,], in the solid state with XeOF, yields Xe02F2 efficiently'? XeOF, -Xe02F2 2FN02 [NO,] [NO,] (j)
+
+
Excess N2O5 produces XeO,. Phosphoryl fluoride reacts with XeF6 efficiently yielding XeOF416: P(O)F,
+ XeF6-
XeOF4
+ PF,
(k)
Stoichiometric reactant quantities at - 196°Creact at RT for 2 h, giving 100% yield. The products are separated by fractional condensation or complexation of PF5 with NaF. This method largely avoids the danger of forming Xe03. Group IA metal sulfonates are carboxylates react with XeF2 when catalyzed by BF317:
-
XeF2 + M+OR-XeF2
+ M'OR-
B F 3 ' OMe2 BF3.OMe
FXeOR
(R = S02CF3or S0,C4F9)
(1)
Xe(OR),
(R = COF, or COC2F5)
(4
The highly electronegative O:IF40 group can replace an F atom in XeF218: 2XeF2 + (I02F4)2-
XeF2 + (I0,F4)2
2FXe(OIOF4)
(cis and trans)
(trans-trans, cis-trans, and cis-cis)
Xe(OIOF4)2
(4 (0)
Bis(trifluoromethy1) sulfoxide forms a Xe-0 bond with [XeF] [SbF;] when mixed in H F at -65°C over 12 h": (CF,),S=O
+ [Xel [SbF61/[(CF3)2S-O-XeF]
[SbF6]
(PI
The solid decomposes exposively above -78°C if mechanically shocked. Compounds FXeOWF5 .xWOF4 (x = 1 or 2) have been observed in equilibrium with F-bridged species in solutions of the complex XeF2.2WOF4in S02ClF containing excess W0Fd2O. The first 0-Xe-F species containing an alkyl (electron-donating) substituent is claimed as an intermediate in a regioselective alkene mechanism2':
MeOH
+ XeF,
It decomposes to H 2 C 0 , Xe, and HF. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.
-
[MeOXeF]
+ HF
(9)
(M. L. THOMPSON) D. F. Smith, Science, 140, 899 (1963). B. Jaselskis, T. M. Spittler, J. L. Huston, J . Am. Chem. Soc., 88, 2149 (1966). J. G. Malm, F. Schreiner, D. W. Osborne, Inorg. Nucl. Chem. Lett., I , 97 (1965). J. L. Huston, J . Phys. Chem., 71, 3339 (1967). R. J. Gillespie, G. J. Schrobilgen, Inorg. Chem., 13, 2370 (1974). S. M. Williamson, C. W. Koch, Science, 139, 1046 (1963). J. S. Ogden, J. J. Turner, J . Chem. Soc., Chem. Cornmun., 693 (1966). E. Jacob, R. Opferkuch, Angew.. Chem., 88, 190 (1976). R. J. Gillespie, G. J. Schrobilgen, J . Chem. Soc., Chern. Commun., 595 (1977). E. H. Appelman, J. G. Malm, J . Am. Chem. Soc., 86, 2141 (1964). H. Selig, H. H. Claassen, C. L. Chernick, J. G. Malm, J. L. Huston, Science, 143, 1322 (1964). J. L. Huston, Inorg. Nucl. Chern. Lett., 4, 29 (1968). C. L. Chernick, H. H. Claassen, J. G . Malm, P. L. Plurien, in Noble Gas Compounds, H. H. Hyman, ed., University of Chicago Press, Chicago, 1963, p. 196.
3.9 Bond Between Group VIB and Group 0 Elements 3.9.3 By Reaction of XeF, and Oxyfluorides with Oxyacids 14. 15. 16. 17. 18. 19. 20. 21.
127
K. 0. Christe, W. W. Wilson, Inorg. Chem., 27, 1296 (1988). K. 0. Christe, W. W. Wilson, Inorg. Chem., 27, 3763 (1988). J. B. Nielsen, S. A. Kinkead, P. G. Filler, Inorg. Chem., 29, 3621 (1990). B. Cremer-Lober, H. Butler, K. Naumann, W. Tyrra, 2. Anorg. Allg. Chem., 607, 34 (1992). R. G. Syvret, G. J. Schrobilgen, J . Chem. Soc., Chem. Commun.,21, 1529 (1985). R. Minkwitz, W. Molsbeck, Z . Anorg. Allg. Chem., 612, 35 (1992). J. H. Holloway, G. J. Schrobilgen, Inorg. Chem., 19, 2632 (1980). D. F. Shellhamer, C. M. Curtis, R. H. Dunham, D. R. Hollingsworth, M. L. Ragains, R. E. Richardson, V. L. Heasley, S.A. Shackelford, G. E. Heasley, J . Org. Chem., 50, 2751 (1985).
3.9.3 By Reaction of Xenon Fluorides and Oxyfluorides with Oxyacids and Their Derivatives' Most stable compounds are formed with HOTeF, and HOSeF,. Compounds formed with H S 0 3 F and HP02F2 are less stable, decomposing at or below RT. Compounds formed with H N 0 3 , HC104, CF3S03H,CH3S03H, and CF3C02Hare all dangerously explosive'. The exceptional thermal stability of the pentafluoroselenates and pentafluorotellurates is attributed to instability of the free radicals OSeF, and OTeF,, a first decomposition product. Electron withdrawal by the five F atoms imparts a great effective electronegativity to the ligands'. These species decompose to the stable peroxide linkage: Xe(OSeF,), Xe(OTeF,),
--
+ F,SeOOSeFj Xe + FjTeOOTeF, Xe
(a) (b)
There is no simple oxide or oxyfluoride of Xe(I1) known, but XeF, reacts with strong protic oxyacids (HOR) yielding nonvolatile compounds of type FXeOR and Xe(OR)zZ-6. These are generally prepared by reaction between stoichiometric quantities of XeF, and the appropriate acid at ca. - 80°C; the H F by-product is removed at low temperature. The FXeOSeF5 and Xe(OSeFI), can be prepared from XeF, and appropriate quantities of HOSeFj7, as with the corresponding Te compounds8. Compounds of type Xe(OR)* are usually less stable than those of type FXeOR. The mixed compound Xe(OTeF,)(OSeF,) is present in CC13F solutions as part of an equilibrium mixture'. Xe(OTeF,),
+ Xe(OSeFJ2 % 2Xe(OTeF,)(OSeF,)
-
(4
A polymeric product results when XeF, reacts with cis-(OH),TeF, at - 196"C10 XeF,
+ cis-(OH),TeF,
n-C,F,-SO,F
+ HF
-(Xe-0-TeF4-0-)-x
(d)
The faintly yellow solid is insoluble in common solvents and decomposes > 80°C to Xe, 0 2 and , TeF,. The salts [(FXeOSOFOXeF)] [AsF,] and [XeOTeF,][AsF,] result from reaction of FXeOS0,F and FXeOTeFj, respectively, with A S F , ~ . ~ . When R is an electron-attracting group, compounds of formula B(OR)3 are excellent ligand transfer agents with group 0 fluorides, thus offering further synthetic possibilities. Xenon tetrafluoride reacts with excess of B(OTeF& in n-C6HI4, yielding Xe(OTeF,),' ': 3XeF4 + 4B(OTeF,),
-
3Xe(OTeF,),
+ 4BF3
(4
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.9 Bond Between Group VIB and Group 0 Elements 3.9.3 By Reaction of XeF, and Oxyfluorides with Oxyacids 14. 15. 16. 17. 18. 19. 20. 21.
127
K. 0. Christe, W. W. Wilson, Inorg. Chem., 27, 1296 (1988). K. 0. Christe, W. W. Wilson, Inorg. Chem., 27, 3763 (1988). J. B. Nielsen, S. A. Kinkead, P. G. Filler, Inorg. Chem., 29, 3621 (1990). B. Cremer-Lober, H. Butler, K. Naumann, W. Tyrra, 2. Anorg. Allg. Chem., 607, 34 (1992). R. G. Syvret, G. J. Schrobilgen, J . Chem. Soc., Chem. Commun.,21, 1529 (1985). R. Minkwitz, W. Molsbeck, Z . Anorg. Allg. Chem., 612, 35 (1992). J. H. Holloway, G. J. Schrobilgen, Inorg. Chem., 19, 2632 (1980). D. F. Shellhamer, C. M. Curtis, R. H. Dunham, D. R. Hollingsworth, M. L. Ragains, R. E. Richardson, V. L. Heasley, S.A. Shackelford, G. E. Heasley, J . Org. Chem., 50, 2751 (1985).
3.9.3 By Reaction of Xenon Fluorides and Oxyfluorides with Oxyacids and Their Derivatives' Most stable compounds are formed with HOTeF, and HOSeF,. Compounds formed with H S 0 3 F and HP02F2 are less stable, decomposing at or below RT. Compounds formed with H N 0 3 , HC104, CF3S03H,CH3S03H, and CF3C02Hare all dangerously explosive'. The exceptional thermal stability of the pentafluoroselenates and pentafluorotellurates is attributed to instability of the free radicals OSeF, and OTeF,, a first decomposition product. Electron withdrawal by the five F atoms imparts a great effective electronegativity to the ligands'. These species decompose to the stable peroxide linkage: Xe(OSeF,), Xe(OTeF,),
--
+ F,SeOOSeFj Xe + FjTeOOTeF, Xe
(a) (b)
There is no simple oxide or oxyfluoride of Xe(I1) known, but XeF, reacts with strong protic oxyacids (HOR) yielding nonvolatile compounds of type FXeOR and Xe(OR)zZ-6. These are generally prepared by reaction between stoichiometric quantities of XeF, and the appropriate acid at ca. - 80°C; the H F by-product is removed at low temperature. The FXeOSeF5 and Xe(OSeFI), can be prepared from XeF, and appropriate quantities of HOSeFj7, as with the corresponding Te compounds8. Compounds of type Xe(OR)* are usually less stable than those of type FXeOR. The mixed compound Xe(OTeF,)(OSeF,) is present in CC13F solutions as part of an equilibrium mixture'. Xe(OTeF,),
+ Xe(OSeFJ2 % 2Xe(OTeF,)(OSeF,)
-
(4
A polymeric product results when XeF, reacts with cis-(OH),TeF, at - 196"C10 XeF,
+ cis-(OH),TeF,
n-C,F,-SO,F
+ HF
-(Xe-0-TeF4-0-)-x
(d)
The faintly yellow solid is insoluble in common solvents and decomposes > 80°C to Xe, 0 2 and , TeF,. The salts [(FXeOSOFOXeF)] [AsF,] and [XeOTeF,][AsF,] result from reaction of FXeOS0,F and FXeOTeFj, respectively, with A S F , ~ . ~ . When R is an electron-attracting group, compounds of formula B(OR)3 are excellent ligand transfer agents with group 0 fluorides, thus offering further synthetic possibilities. Xenon tetrafluoride reacts with excess of B(OTeF& in n-C6HI4, yielding Xe(OTeF,),' ': 3XeF4 + 4B(OTeF,),
-
3Xe(OTeF,),
+ 4BF3
(4
128
3.9 Bond Between Group VIB and Group 0 Elements 3.9.3 By Reaction of XeF, and Oxyfluorides with Oxyacids ~~~
Reaction occurs as the solution warms from -78°C to RT over the course of several hours, after which the BF3 is removed along with any unreacted starting material. This compound, which decomposes rapidly at its 72°C melting point, is the only wellcharacterized Xe(1V) compound of its type. The Xe(V1) compounds OXe(OTeF5), and Xe(OTeF,), are prepared by reaction of XeOF4 and XeF6, respectively, with excess B(OTeFJ3 in n-C5F1293'23'3:
+ 2B(OTeF,), 3XeOF4 + 4B(OTeF,), XeF,
--
+ 2BF3 30Xe(OTeF5), + 4BF3
(f 1
Xe(OTeF,),
(€9
The procedure is like that for the preparation of Xe(OTeF,),. Reaction (f) takes place in 3 days at -50°C. Reaction (g) occurs upon gradual warming from -65°C to -25°C. The stability order is Xe(oTeF& < Xe(OTeF,), < OXe(OTeF,),. If excess XeF, or XeOF, is used, mixtures of compounds of type XeF,(OTeF,), --x and OXeF,(OTeF,),-, form, where x = 1, 2 (cis and trans), and 3, identified by their N M R spectra',. Other R groups can also be e r n p l ~ y e d ' ~ :
--
+ B(OR)3 3XeF, + 2B(OR), 3XeFz
+ BF3 (R = S02CF3) 3Xe(OR), + 2BF3 (R = COCF,) 3FXeOR
(h) (i)
Several cationic species containing the Xe-(OTeF,) moiety have been reported, but they d o not offer new methodologies for making Xe-0 bonds15. The acid F S 0 3 H reacts with XeF, with elimination of HF4:
+ HOS0,FXeFz + 2HOS02F-
FXeOSOzF + HF
XeF,
Xe(OS02F),
(j)
+ 2HF
(k)
N o such derivatives of Xe(1V) exist,. Xenon hexafluoride with a stoichiometric amount of H S 0 , F yields XeF5(OSOzF)5.Reagents are mixed at -22"C, and the mixture is warmed to - 5°C during 3 days. The compound decomposes at elevated temperatures ( >73°C) to the peroxydisulfuryl difluoride: F,XeOS02F
+ 5HOS02F-
Xe
+ 5HF + 3S,0,F2
(1)
Eventhough the solid has a NaCl structure, it has substantial volatility', indicating either a covalent gaseous species containing the Xe-0 bond or a reversible decomposition into XeF, plus SO3 in the gas phase. No further substitution occurs with excess H S 0 3 F . A claimed synthesis of F4Xe(OS02F)216was subsequently withdrawn, as was that of F,Xe( 0S 0 F), ,. CF3C(0)NH, is protonated with HF in the presence of AsF, in H F and reacts with XeF, in BrF, between -62 and -55T''. [CF,C(OH)NH,] [AsF,]
+ XeF,
-
[CF3(OXeF)NH,] [AsF,]
+ HF
(m)
The unstable compound Xe(CF3C02), is claimed from reaction between XeF, and CF3C02H dissolved in (CF,CO),O at -2O"C, followed by cooling to -40°C to precipitate a solid product". Identification was only by mass spectrometry and it is possible that the observed species was actually a Xe(I1) compound'. (M. L. THOMPSON)
3.9 Bond Between Group VIE and Group 0 Elements 3.9.4 Bonds Between Oxygen and Krypton or Radon
129
1. For a review of compounds of this type, see K. Seppelt, D. Lentz, Prog. Inorg. Chem., 29, 167 (1982). 2. N. Bartlett, M. Wechsberg, F. 0. Sladky, P. A. Bulliner, G. R. Jones, R. D. Burbank, J . Chem. Soc., Chem. Commun., 703 (1969). 3. F. 0. Sladky, Monatsh. Chem., 101, 1559, 1571, 1578 (1970). 4. M. Wechsberg, P. A. Bulliner, F. 0.Sladky, R. Mews, N. Bartlett, Inorg. Chem., 11, 3063 (1972). 5. M. Eisenberg, D. D. DesMarteau, Inorg. Chem., 11, 1901 (1972). 6. K. Seppelt, H. Rupp, Z . Anorg. Allg. Chem., 409, 338 (1974). 7. K. Seppelt, Angew. Chem., Intl. Ed. Engl., 11, 723 (1972). 8. F. Sladky, Angew. Chem., Int. Ed. Engl., 8, 373, 523 (1969). 9. K. Seppelt, D. Nothe, Inorg. Chem., 12,2727 (1973). 10. L. Turowsky, K. Seppelt, Inorg. Chem., 29, 3226 (1990). 11. E. Jacob, D. Lentz, K. Seppelt, Z . Anorg. Allg. Chem., 472, 7 (1981). 12. D. Lentz, K. Seppelt, Angew. Chem., 91, 68 (1979). 13. G. A. Shumacher, G. J. Schrobilgen, Inorg. Chem., 23, 2923 (1984). 14. B. Cremer-Lober, H. Butler, D. Naumann, W. Tyrra, Z . Anorg. Allg. Chem., 607, 34 (1992). 15. R. G. Syvret, K. M. Mitchell, J. C. P. Sanders, G. J. Schrobilgen, Inorg. Chem., 31,3381 (1992). 16. M. Eisenberg, D. D. DesMarteau, J . Am. Chem. Soc., 92, 4759 (1970). 17. G. J. Schrobilgen, J. M. Whalen, Inorg. Chem., 33, 5207 (1994). 18. A. Iskraut, R. Taubenest, E. Schumacher, Chimia, 18, 188 (1964).
3.9.4 Bonds Between Oxygen and Krypton or Radon The first well-characterized Kr-0 bond report, is the result of B(OTeF& reaction with KrF, at -90 to -112°C in SO2C1F’. The thermally unstable compound was characterized by 19F and 170NMR spectroscopy. 3KrF2
+ 2B(OTeF&
-
3Kr(OTeFS),
+ 2BF3
(a)
Attempts to isolate Kr(OTeF& via a similar reaction led to decomposition, resulting in Kr and FsTeOOTeFs2. One claim of “kryptic acid” formation in aqueous solution3 has not been substantiated and is likely incorrect. Studies by tracer and Mossbauer techniques of the /3 decay of ‘jBr incorporated into BrO; gives no evidence of the formation of KrOj4.’. There is no fundamental reason why Rn-0 compounds cannot be made. By analogy with Xe chemistry, any simple oxides or oxyfluorides of Rn will be derived from RnF, and RnF,, whereas there is considerable evidence that the only radon fluoride identified as of this time is RnF, (Section 2.10). An early report of oxidized Rn in aqueous solution6 was subsequently refuted7, but a report claiming production and hydrolysis of RnF, or RnF6 to give aqueous RnOj8 remains to be either substantiated o r disproved. There are no reports of oxyradon compound preparation by reaction of RnF2 with strong oxyacids or their derivatives. (M. L. THOMPSON) 1. J. C . P. Sanders, G. J. Schrobilgen, J . Chem. Soc., Chem. Commun., 1576 (1989); A. G. Streng, A. V. Grosse, Science, 143, 242 (1964).
2. E. Jacob, D. Lentz, K. Seppelt, Z. Anorg. Allg. Chem., 472, 7 (1981). 3. A. G. Streng, A. V. Grosse, Science, 143, 242 (1964). 4. A. N. Murin, V. D. Nefedov, I. S. Kirin, S. A. Grachev, Y . K. Gusev, G. N. Shapkin, Zh. Obsch. Khim., 35, 2137 (1965). 5. M. Pasternak, T. Sonnino, Phys. Rev., 164, 384 (1967). 6. M. W. Hazeltine, H. C. Moser, J . Am. Chem. Soc., 89. 2497 (1967). 7. K. Flohr, E. H. Appelman, J . Am. Chem. SOC.,90, 3584 (1968). 8. V. V. Avrorin, R. N. Krasikova, V. D. Nefedov, M. A. Toropova, Radiokhimiya, 23, 879 (1981).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.9 Bond Between Group VIE and Group 0 Elements 3.9.4 Bonds Between Oxygen and Krypton or Radon
129
1. For a review of compounds of this type, see K. Seppelt, D. Lentz, Prog. Inorg. Chem., 29, 167 (1982). 2. N. Bartlett, M. Wechsberg, F. 0. Sladky, P. A. Bulliner, G. R. Jones, R. D. Burbank, J . Chem. Soc., Chem. Commun., 703 (1969). 3. F. 0. Sladky, Monatsh. Chem., 101, 1559, 1571, 1578 (1970). 4. M. Wechsberg, P. A. Bulliner, F. 0.Sladky, R. Mews, N. Bartlett, Inorg. Chem., 11, 3063 (1972). 5. M. Eisenberg, D. D. DesMarteau, Inorg. Chem., 11, 1901 (1972). 6. K. Seppelt, H. Rupp, Z . Anorg. Allg. Chem., 409, 338 (1974). 7. K. Seppelt, Angew. Chem., Intl. Ed. Engl., 11, 723 (1972). 8. F. Sladky, Angew. Chem., Int. Ed. Engl., 8, 373, 523 (1969). 9. K. Seppelt, D. Nothe, Inorg. Chem., 12,2727 (1973). 10. L. Turowsky, K. Seppelt, Inorg. Chem., 29, 3226 (1990). 11. E. Jacob, D. Lentz, K. Seppelt, Z . Anorg. Allg. Chem., 472, 7 (1981). 12. D. Lentz, K. Seppelt, Angew. Chem., 91, 68 (1979). 13. G. A. Shumacher, G. J. Schrobilgen, Inorg. Chem., 23, 2923 (1984). 14. B. Cremer-Lober, H. Butler, D. Naumann, W. Tyrra, Z . Anorg. Allg. Chem., 607, 34 (1992). 15. R. G. Syvret, K. M. Mitchell, J. C. P. Sanders, G. J. Schrobilgen, Inorg. Chem., 31,3381 (1992). 16. M. Eisenberg, D. D. DesMarteau, J . Am. Chem. Soc., 92, 4759 (1970). 17. G. J. Schrobilgen, J. M. Whalen, Inorg. Chem., 33, 5207 (1994). 18. A. Iskraut, R. Taubenest, E. Schumacher, Chimia, 18, 188 (1964).
3.9.4 Bonds Between Oxygen and Krypton or Radon The first well-characterized Kr-0 bond report, is the result of B(OTeF& reaction with KrF, at -90 to -112°C in SO2C1F’. The thermally unstable compound was characterized by 19F and 170NMR spectroscopy. 3KrF2
+ 2B(OTeF&
-
3Kr(OTeFS),
+ 2BF3
(a)
Attempts to isolate Kr(OTeF& via a similar reaction led to decomposition, resulting in Kr and FsTeOOTeFs2. One claim of “kryptic acid” formation in aqueous solution3 has not been substantiated and is likely incorrect. Studies by tracer and Mossbauer techniques of the /3 decay of ‘jBr incorporated into BrO; gives no evidence of the formation of KrOj4.’. There is no fundamental reason why Rn-0 compounds cannot be made. By analogy with Xe chemistry, any simple oxides or oxyfluorides of Rn will be derived from RnF, and RnF,, whereas there is considerable evidence that the only radon fluoride identified as of this time is RnF, (Section 2.10). An early report of oxidized Rn in aqueous solution6 was subsequently refuted7, but a report claiming production and hydrolysis of RnF, or RnF6 to give aqueous RnOj8 remains to be either substantiated o r disproved. There are no reports of oxyradon compound preparation by reaction of RnF2 with strong oxyacids or their derivatives. (M. L. THOMPSON) 1. J. C . P. Sanders, G. J. Schrobilgen, J . Chem. Soc., Chem. Commun., 1576 (1989); A. G. Streng, A. V. Grosse, Science, 143, 242 (1964).
2. E. Jacob, D. Lentz, K. Seppelt, Z. Anorg. Allg. Chem., 472, 7 (1981). 3. A. G. Streng, A. V. Grosse, Science, 143, 242 (1964). 4. A. N. Murin, V. D. Nefedov, I. S. Kirin, S. A. Grachev, Y . K. Gusev, G. N. Shapkin, Zh. Obsch. Khim., 35, 2137 (1965). 5. M. Pasternak, T. Sonnino, Phys. Rev., 164, 384 (1967). 6. M. W. Hazeltine, H. C. Moser, J . Am. Chem. Soc., 89. 2497 (1967). 7. K. Flohr, E. H. Appelman, J . Am. Chem. SOC.,90, 3584 (1968). 8. V. V. Avrorin, R. N. Krasikova, V. D. Nefedov, M. A. Toropova, Radiokhimiya, 23, 879 (1981).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 0 Formation of Non-stoichiometric Oxides 3.1 0.1 introduction The sections that follow deal with structure and structural principles in the solid state and with the synthesis of solid state oxides. The oxides discussed are important in various contexts, including the large area of materials applications. (A. D. NORMAN)
3.10.1.1 Basic Defect Equilibria: Thermodynamic and Structural Principles 3.10.1.1.1 Inherent Point Defect and Electron Band Equilibria
The real structure of solids differs from the perfectly periodic one deduced from X-ray diffraction. In the simplest cases the defects in the real structure are misplaced atoms or point defects. An atom missing from a site normally occupied in the ideal structure is a vacancy, and an atom occupying a normally empty site is an interstitial. An atom on a wrong site (e.g.,a Zn atom on a Cu site in CuZn) is an antistructure defect. This last defect is unlikely to be of importance in oxides. Whether deliberately introduced or not, foreign atoms, i.e., atoms of the wrong kind (e.g., Fe in MgO) are inevitably present in small concentrations-and their presence can affect the properties. In the definitive treatment of the defect chemistry of solids', the notation consists of a main symbol, which is either the symbol of an element or V (for vacancy); a subscript, to indicate the site (I for interstitial); and a superscript (dots, vertical lines, or a cross), to indicate the effective charge ( + , - or 0, respectively) of the defect relative to that at the site in the ideal crystal. Thus a missing Ni2' in NiO is symbolized Vki (effective charge -2). A Zn2+ in an interstitital site in ZnO is represented by Zn;'. A missing C1- ion in KCl is Vc1;this defect may trap an electron to produce the well-known F-center, V& A Li+ ion on a Ni2+ site in NiO is LiLi. Other examples appear below. In addition to structural defects, electronic defects (either extra or missing electrons) must be considered. Missing electrons are holes (symbol h') and their concentration is denoted p . Likewise the concentration of extra electrons is n, and their symbol is e'. A hole e.g., might be a Ni3+ ion on a Ni2+ site in NiO. In ionic crystals, electronic defects are localized at a site by virtue of the polarization they induce in the surrounding crystal, and they are then termed polarons. Defects behave as separate entities in a solution', and thus the methods of ionic solution theory can be used. The treatment for low concentrations of defects in an oxide, MO is outlined; the generalization to other stoichiometries is straightforward'. Consider the formation of cation and anion vacancies in a perfect crystal. This is analogous to ionization of a solvent and, just as one cannot produce an H f ion without a counterion, so in a crystal must charge neutrality also be maintained. Cation vacancies
130
3.10.1 Introduction 131 3.10.1.1 Basic Defect Equilibria: Thermodynamic and Structural Principles 3.10.1.1.1 Inherent Point Defect and Electron Band Equilibria
Vh cannot be produced alone. Thus vacancy pairs are produced by:
+ v;
O-VA
(a)
Here the zero symbolizes the perfect crystal. For this process the equilibrium constant is: = K$
[VL] [V;]
(b)
For the formation of singly charged vacancies:
0-
VL
+ v;,
(4
and the analogous equilibrium constant is: CVMl CV;,l
= KI,
Vacancies may also be formed by moving an atom into an interstitial site: O-V&+M;'
(el
with CVLl [M;'I
=
K F
(f)
The intrinsic formation of electrons and holes by excitation of an electron from the highest energy band of occupied levels (valence band) to the lowest energy band of empty levels (conduction band) must also be considered: O-e'+h' np
=
(g)
Ki
(h)
The energy gap E G between the valence and conduction band is large in the ionic oxides, so that Ki, which varies as exp(- EGIRT), is small. Hence, in stoichiometric oxides the electron and hole concentrations are also small. However, some oxides (e.g., TiO, C r 0 2 , and ReO,) have partly filled bands and are metallic conductors. Equations (g) and (h) are not applicable in such instances. Defects may change their oxidation state (i.e., act as electron donors or acceptors) and one must consider further equilibria such as: Vg-
VL
+ h'
6)
For this process: CVMl- K1
P--
cvw
An additional constraint on defect concentrations is the electrical neutrality condition, which states that the number of effectively positive charges is equal to the number of effectively negative charges. For the defects enumerated above, this becomes: 2CM;'I
+ 2CV;l + CVbl + n = 2CVLI + [VLl + p
(k)
If foreign atoms with effective charges are present, their concentrations must also be included. Because of the presence of their concentrations in the electrical neutrality constraint, foreign atoms can affect the concentrations of defects.
132 3.10.1 Introduction 3.10.1.1 Basic Defect Equilibria: Thermodynamic and Structural Principles 3.10.1.1.2 External Equilibrium with Oxygen Fugacity
The concentrations of the seven defects appearing in Eq. (k) are constrained by six equations [(b), (d), (f), (h), (j), and (k)] and are thus so far indeterminate. One way to remove this indeterminacy is to require that the crystal be stoichiometric (number of metal atoms equal to the number of oxygen atoms). In terms of defect concentrations, this translates into: However, this is an arbitrary constraint. The correct procedure is to allow the crystal to come into equilibrium with its surroundings. (M. O'KEEFFE)
1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd. ed., North-Holland, Amsterdam, 1973. Volume 2 of this three-volume work is the definitive treatment of point defect equilibria. 3.10.1 .1.2 External Equilibrium with Oxygen Fugacity
Relaxing the constraint of perfect stoichiometry, the formula of the crystal is written M1-dO, where 6 is positive or negative and, for the treatment in this section to be applicable 6 < 1. At given values of T, P, and 6, the activities (fugacities) of M(g) and O,(g) in the atmosphere, fv and fo2,are related through the equilibrium:
MO(s)= M(g) + +O&)
(4
where AG is the standard free energy change for reaction (a). Only the relationship between 6 and fo2 needs to be explored; i.e., an equation is needed that will replace equation (1) of 3.10.1.1.1, and in which the concentration of one defect species is related to oxygen fugacity. This may be, e.g.: +02(g)-
0 0
+ VM + 2h'
(4
PZ CVMl -- Kox
fd;2
Provided all the equilibrium constants are known, equation (d) together with the equations in 3.10.1.1.1 allow all defect concentrations (hence 6) to be calculated as a function of oxygen fugacity. Sometimes (e.g., in the case of ZnO) it is more convenient to consider metal solution in the oxide by, e.g.: M(g)-
M;'
n2[M;*] -fM
+ 2e'
- KM
This expression contains no new information, since: KM =
K ~ K , ~ (K;~K~/~)
(el
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
132 3.10.1 Introduction 3.10.1.1 Basic Defect Equilibria: Thermodynamic and Structural Principles 3.10.1.1.2 External Equilibrium with Oxygen Fugacity
The concentrations of the seven defects appearing in Eq. (k) are constrained by six equations [(b), (d), (f), (h), (j), and (k)] and are thus so far indeterminate. One way to remove this indeterminacy is to require that the crystal be stoichiometric (number of metal atoms equal to the number of oxygen atoms). In terms of defect concentrations, this translates into: However, this is an arbitrary constraint. The correct procedure is to allow the crystal to come into equilibrium with its surroundings. (M. O'KEEFFE)
1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd. ed., North-Holland, Amsterdam, 1973. Volume 2 of this three-volume work is the definitive treatment of point defect equilibria. 3.10.1 .1.2 External Equilibrium with Oxygen Fugacity
Relaxing the constraint of perfect stoichiometry, the formula of the crystal is written M1-dO, where 6 is positive or negative and, for the treatment in this section to be applicable 6 < 1. At given values of T, P, and 6, the activities (fugacities) of M(g) and O,(g) in the atmosphere, fv and fo2,are related through the equilibrium:
MO(s)= M(g) + +O&)
(4
where AG is the standard free energy change for reaction (a). Only the relationship between 6 and fo2 needs to be explored; i.e., an equation is needed that will replace equation (1) of 3.10.1.1.1, and in which the concentration of one defect species is related to oxygen fugacity. This may be, e.g.: +02(g)-
0 0
+ VM + 2h'
(4
PZ CVMl -- Kox
fd;2
Provided all the equilibrium constants are known, equation (d) together with the equations in 3.10.1.1.1 allow all defect concentrations (hence 6) to be calculated as a function of oxygen fugacity. Sometimes (e.g., in the case of ZnO) it is more convenient to consider metal solution in the oxide by, e.g.: M(g)-
M;'
n2[M;*] -fM
+ 2e'
- KM
This expression contains no new information, since: KM =
K ~ K , ~ (K;~K~/~)
(el
3.10.1 Introduction 133 3.10.1.1 Basic Defect Equilibria: Thermodynamic and Structural Principles 3.10.1.1.3 Relations Between Nonstoichiometry and Physical Properties
In practice, just as in solution chemistry, the concentrations of a few defects are larger than the rest. This simplifies the neutrality condition and makes the solution of the system of equations easier; e.g., in NiO at high temperature the predominant defects are Vhi and h’. Equation (k) in 3.10.1.1 now becomes 2[VNi]
=p
and eq. (d) may be replaced by This is an expression that may be verified experimentally. In COO and especially MnO, as fo2 (hence 6) increases, there is transfer to a regime in which the dominant defects are Vh and h’ then, in contrast to equation (i):
6 = PMl=
Kox (K) fdl”
as is observed experimentally. In the region offo2 (hence 6) corresponding to the transition between the two regimes, the neutrality condition is
2[VM]
+ [VM]
=p
resulting in slightly more complicated, but still tractable, expressions for the dependence of oxygen fugacity on stoichiometry and defect concentrations. Diagrams representing the variation of defect concentration with fo, (or more generally, with the activity of one component of a compound) are available. Although cation vacancies are the majority defect in many oxides, in others such as ZnO, interstitials (Zn;’) predominate. In F e 3 0 4 at low f o , iron interstitials dominate, whereas at high f o , iron vacancies are dominant. In oxides with the fluorite structure anion, interstitials are the most important. In oxides with only a small stoichiometry range (e.g., MgO, A1203), with only one stable oxidation state of the cation, the defect concentrations in materials prepared are determined by the presence of aliovalent foreign atoms, except near the melting point. Reviews of point defects in oxides are available’s*. (M. O’KEEFFE)
1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd rev. ed., North-Holland, Amsterdam,
1973. 2. P. Kofstad, Nonstoichiometry, Diffusion, and Electrical Conductivity, in Binary Metal Oxides, A comprehensiveaccount of defect structure in binary metal oxides. Wiley, New York, 1972. An excellent account of diffusion-controlledreactions and of defect equilibria in ternary, etc., oxides is given by H. Schmalzried, Solid State Reactions, 2nd ed., Verlag Chemie, Weinheim, 1981. 3.10.1.1.3 Relations Between Nonstoichiometry and Physical Properties
Mass transport in oxides proceeds by a defect (vacancy or interstitial) motion, hence is affected by the degree of nonstoichiometry. At low defect concentrations, the diffusion coefficient of an atom is proportional to the defect concentration. Diffusion coefficients, therefore, depend on oxygen fugacity in a predictable way, and this dependence is important in defect chemistry. Since ionic conductivity is closely related to diffusivity the preceding statements apply to oxides in which ionic (rather than electronic) conductivity predominates.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.1 Introduction 133 3.10.1.1 Basic Defect Equilibria: Thermodynamic and Structural Principles 3.10.1.1.3 Relations Between Nonstoichiometry and Physical Properties
In practice, just as in solution chemistry, the concentrations of a few defects are larger than the rest. This simplifies the neutrality condition and makes the solution of the system of equations easier; e.g., in NiO at high temperature the predominant defects are Vhi and h’. Equation (k) in 3.10.1.1 now becomes 2[VNi]
=p
and eq. (d) may be replaced by This is an expression that may be verified experimentally. In COO and especially MnO, as fo2 (hence 6) increases, there is transfer to a regime in which the dominant defects are Vh and h’ then, in contrast to equation (i):
6 = PMl=
Kox (K) fdl”
as is observed experimentally. In the region offo2 (hence 6) corresponding to the transition between the two regimes, the neutrality condition is
2[VM]
+ [VM]
=p
resulting in slightly more complicated, but still tractable, expressions for the dependence of oxygen fugacity on stoichiometry and defect concentrations. Diagrams representing the variation of defect concentration with fo, (or more generally, with the activity of one component of a compound) are available. Although cation vacancies are the majority defect in many oxides, in others such as ZnO, interstitials (Zn;’) predominate. In F e 3 0 4 at low f o , iron interstitials dominate, whereas at high f o , iron vacancies are dominant. In oxides with the fluorite structure anion, interstitials are the most important. In oxides with only a small stoichiometry range (e.g., MgO, A1203), with only one stable oxidation state of the cation, the defect concentrations in materials prepared are determined by the presence of aliovalent foreign atoms, except near the melting point. Reviews of point defects in oxides are available’s*. (M. O’KEEFFE)
1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd rev. ed., North-Holland, Amsterdam,
1973. 2. P. Kofstad, Nonstoichiometry, Diffusion, and Electrical Conductivity, in Binary Metal Oxides, A comprehensiveaccount of defect structure in binary metal oxides. Wiley, New York, 1972. An excellent account of diffusion-controlledreactions and of defect equilibria in ternary, etc., oxides is given by H. Schmalzried, Solid State Reactions, 2nd ed., Verlag Chemie, Weinheim, 1981. 3.10.1.1.3 Relations Between Nonstoichiometry and Physical Properties
Mass transport in oxides proceeds by a defect (vacancy or interstitial) motion, hence is affected by the degree of nonstoichiometry. At low defect concentrations, the diffusion coefficient of an atom is proportional to the defect concentration. Diffusion coefficients, therefore, depend on oxygen fugacity in a predictable way, and this dependence is important in defect chemistry. Since ionic conductivity is closely related to diffusivity the preceding statements apply to oxides in which ionic (rather than electronic) conductivity predominates.
134
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.1 Introduction
Rates of solid state reactions such as the oxidation of metals are dependent on the movement of atoms through the product oxide. Ternary, etc., oxides are prepared by solid state reaction of the corresponding oxides (e.g., MgA1204 from M g O and A1203), and the rate is likewise determined by the diffusion of atoms in the product oxide. Nonstoichiometric transition metal oxides are good electronic (electron or hole) conductors, with a conductivity dependent on electron or hole concentration. As these concentrations are again related to oxygen fugacity, electrical conductivity also provides a probe of defect structure in oxides’. (M. O’KEEFFE) 1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd ed., North-Holland, Amsterdam, 1973.
3.10.1.2 Nonstoichiometry and Shear Planes
The field of defect interactions in solids is a major area of solid state physics and chemistry. Point defects, formed either as charge compensators for impurities or by thermal generation at high temperatures, may be trapped by impurity ions or by oxidized or reduced cations in nonstoichiometric phases. Structural properties of the resulting complexes have been reviewed’, and a discussion of the effect of defect interactions on transport is available’. The following account concentrates on one of the most important and relevant aspects of defect interactions, which leads to extended defect formation, the study of which has been a particularly active area of research in recent years. (C. R. A. CATLOW) 1. C. R. A. Catlow, in Non-stoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, (1982). 2. F. Bkniere, C. R. A. Catlow, Mass Transport in Solids, Plenum Press, New York, 1983.
3.10.1.2.1 Introduction
Deviation from stoichiometric composition results in disorder in the crystalline solid. This disorder is based on point defects, either vacancies (as with nonstoichiometric Fe, -,0)’-3 or interstitials (as in nonstoichiometric UOz’ :+ ’, although complex structures often develop in such compounds owing to point defect aggregation-a major topic in contemporary studies of nonstoichiometry6. However, an alternative structural method of incorporating compositional variation is to change the mode of linkage of the metal-oxygen polyhedra from which the crystal is constructed. Thus, in W 0 3 , a compound with a Re03-based structure in which W 0 6 octahedra are corner-linked, reduction of the compound which requires a decrease in the oxygen/metal ratio, can be achieved by replacing corner-sharing by edge-sharing. However, such structural rearrangement cannot be affected for octahedra in isolation. Regions in which the rearrangements take place must be grouped into planes. These are known as crystallographic shear planes and are the basis of the nonstoichiometric compounds W 0 3 - x , MOO^-^, and TiOz-x, where their presence is conclusively demonstrated by electron microscopy’ and diffraction. The origin of the term “shear plane” can be understood by adopting another approach to crystal structure and formation, one that has the advantage of relating shear plane structures to point defects. This is illustrated in Figure 1, which shows a section through the R e 0 3 structure, into which 0 vacancies are introduced by reduction. The
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 134
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.1 Introduction
Rates of solid state reactions such as the oxidation of metals are dependent on the movement of atoms through the product oxide. Ternary, etc., oxides are prepared by solid state reaction of the corresponding oxides (e.g., MgA1204 from M g O and A1203), and the rate is likewise determined by the diffusion of atoms in the product oxide. Nonstoichiometric transition metal oxides are good electronic (electron or hole) conductors, with a conductivity dependent on electron or hole concentration. As these concentrations are again related to oxygen fugacity, electrical conductivity also provides a probe of defect structure in oxides’. (M. O’KEEFFE) 1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd ed., North-Holland, Amsterdam, 1973.
3.10.1.2 Nonstoichiometry and Shear Planes
The field of defect interactions in solids is a major area of solid state physics and chemistry. Point defects, formed either as charge compensators for impurities or by thermal generation at high temperatures, may be trapped by impurity ions or by oxidized or reduced cations in nonstoichiometric phases. Structural properties of the resulting complexes have been reviewed’, and a discussion of the effect of defect interactions on transport is available’. The following account concentrates on one of the most important and relevant aspects of defect interactions, which leads to extended defect formation, the study of which has been a particularly active area of research in recent years. (C. R. A. CATLOW) 1. C. R. A. Catlow, in Non-stoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, (1982). 2. F. Bkniere, C. R. A. Catlow, Mass Transport in Solids, Plenum Press, New York, 1983.
3.10.1.2.1 Introduction
Deviation from stoichiometric composition results in disorder in the crystalline solid. This disorder is based on point defects, either vacancies (as with nonstoichiometric Fe, -,0)’-3 or interstitials (as in nonstoichiometric UOz’ :+ ’, although complex structures often develop in such compounds owing to point defect aggregation-a major topic in contemporary studies of nonstoichiometry6. However, an alternative structural method of incorporating compositional variation is to change the mode of linkage of the metal-oxygen polyhedra from which the crystal is constructed. Thus, in W 0 3 , a compound with a Re03-based structure in which W 0 6 octahedra are corner-linked, reduction of the compound which requires a decrease in the oxygen/metal ratio, can be achieved by replacing corner-sharing by edge-sharing. However, such structural rearrangement cannot be affected for octahedra in isolation. Regions in which the rearrangements take place must be grouped into planes. These are known as crystallographic shear planes and are the basis of the nonstoichiometric compounds W 0 3 - x , MOO^-^, and TiOz-x, where their presence is conclusively demonstrated by electron microscopy’ and diffraction. The origin of the term “shear plane” can be understood by adopting another approach to crystal structure and formation, one that has the advantage of relating shear plane structures to point defects. This is illustrated in Figure 1, which shows a section through the R e 0 3 structure, into which 0 vacancies are introduced by reduction. The
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 134
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.1 Introduction
Rates of solid state reactions such as the oxidation of metals are dependent on the movement of atoms through the product oxide. Ternary, etc., oxides are prepared by solid state reaction of the corresponding oxides (e.g., MgA1204 from M g O and A1203), and the rate is likewise determined by the diffusion of atoms in the product oxide. Nonstoichiometric transition metal oxides are good electronic (electron or hole) conductors, with a conductivity dependent on electron or hole concentration. As these concentrations are again related to oxygen fugacity, electrical conductivity also provides a probe of defect structure in oxides’. (M. O’KEEFFE) 1. F. A. Kroger, The Chemistry of Imperfect Crystals, 2nd ed., North-Holland, Amsterdam, 1973.
3.10.1.2 Nonstoichiometry and Shear Planes
The field of defect interactions in solids is a major area of solid state physics and chemistry. Point defects, formed either as charge compensators for impurities or by thermal generation at high temperatures, may be trapped by impurity ions or by oxidized or reduced cations in nonstoichiometric phases. Structural properties of the resulting complexes have been reviewed’, and a discussion of the effect of defect interactions on transport is available’. The following account concentrates on one of the most important and relevant aspects of defect interactions, which leads to extended defect formation, the study of which has been a particularly active area of research in recent years. (C. R. A. CATLOW) 1. C. R. A. Catlow, in Non-stoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, (1982). 2. F. Bkniere, C. R. A. Catlow, Mass Transport in Solids, Plenum Press, New York, 1983.
3.10.1.2.1 Introduction
Deviation from stoichiometric composition results in disorder in the crystalline solid. This disorder is based on point defects, either vacancies (as with nonstoichiometric Fe, -,0)’-3 or interstitials (as in nonstoichiometric UOz’ :+ ’, although complex structures often develop in such compounds owing to point defect aggregation-a major topic in contemporary studies of nonstoichiometry6. However, an alternative structural method of incorporating compositional variation is to change the mode of linkage of the metal-oxygen polyhedra from which the crystal is constructed. Thus, in W 0 3 , a compound with a Re03-based structure in which W 0 6 octahedra are corner-linked, reduction of the compound which requires a decrease in the oxygen/metal ratio, can be achieved by replacing corner-sharing by edge-sharing. However, such structural rearrangement cannot be affected for octahedra in isolation. Regions in which the rearrangements take place must be grouped into planes. These are known as crystallographic shear planes and are the basis of the nonstoichiometric compounds W 0 3 - x , MOO^-^, and TiOz-x, where their presence is conclusively demonstrated by electron microscopy’ and diffraction. The origin of the term “shear plane” can be understood by adopting another approach to crystal structure and formation, one that has the advantage of relating shear plane structures to point defects. This is illustrated in Figure 1, which shows a section through the R e 0 3 structure, into which 0 vacancies are introduced by reduction. The
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.2 Structural Properties
135
cation oxygen vacancy (oxygen ions at intersections of mesh1
o
(a1
/
direction of shear
ibl
--.- shear plane
(arrows indicate direction for metal re lax0t ions I
Figure 1. Schematic representation of shear plane formation: (a) aligned vacancies in cross section of ReO, structure and (b) shear plane formed by vacancy elimination. alignment of the vacancies (Fig. la) generates a vacancy disk when the structure is extended into three-dimensions. The crucial step now follows: the lower half of the structure (i.e., below the disk) is sheared relative to the top half, in the direction shown in the figure. This leads to a superposition of the starred lattice oxygen ions over the vacancies which are now eliminated, to give a modified structure (Fig. lb). Coherence is restored to the oxygen sublattice, but there is now a planar fault in the metal lattice; the latter corresponds to the (100) shear plane, and Figure l b shows that in the vicinity of the planar defect, corner-sharing of octehedra is replaced by edge-sharing. These two equivalent descriptions are the basic features of shear plane structural chemistry. The study of nonstoichiometric oxides containing these defects concentrates on structural aspects, although attention is paid to fundamental thermodynamic and kinetic factors, especially the factors controlling the stability and interactions of shear planes, the relationship with point defect structures, and the mechanism of shear plane formation. In addition, electrical properties of compounds containing shear planes are studied. Reference to these factors will be made in the discussion that follows.
(C.R. A. CATLOW) F. Koch, J. B. Cohen, Acta Crystallogr., Sect. B, 25, 275 (1969). A. K. Cheetham, B. E. F. Fender, R. I. Taylor, J . Phys., C, 4, 2160 (1971). C. R A. Catlow, B. E. F. Fender, J. Phys., C , 8 , 3267 (1975). B. T. M. Willis, Proc. Br. Ceram. Soc., I , 9 (1964). C. R. A. Catlow, Proc. London, SOC.,Ser. A , 353, 533 (1977). C. R. A. Catlow, in Non-Stoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, 1981. 7. For a general review of microscopic studies of shear-plane-containing oxides see L. A. Bursill, B. G. Hyde, Prog. Solid State Chem., 7, 177 (1972).
1. 2. 3. 4. 5. 6.
3.10.1.2.2 Structural Properties
Shear plane formation is confined to the rutile-structured oxides ( T i 0 2- x and VOz - x ) and Re03-based structures [WO, and MOO,-,I (although MOO, does not
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.2 Structural Properties
135
cation oxygen vacancy (oxygen ions at intersections of mesh1
o
(a1
/
direction of shear
ibl
--.- shear plane
(arrows indicate direction for metal re lax0t ions I
Figure 1. Schematic representation of shear plane formation: (a) aligned vacancies in cross section of ReO, structure and (b) shear plane formed by vacancy elimination. alignment of the vacancies (Fig. la) generates a vacancy disk when the structure is extended into three-dimensions. The crucial step now follows: the lower half of the structure (i.e., below the disk) is sheared relative to the top half, in the direction shown in the figure. This leads to a superposition of the starred lattice oxygen ions over the vacancies which are now eliminated, to give a modified structure (Fig. lb). Coherence is restored to the oxygen sublattice, but there is now a planar fault in the metal lattice; the latter corresponds to the (100) shear plane, and Figure l b shows that in the vicinity of the planar defect, corner-sharing of octehedra is replaced by edge-sharing. These two equivalent descriptions are the basic features of shear plane structural chemistry. The study of nonstoichiometric oxides containing these defects concentrates on structural aspects, although attention is paid to fundamental thermodynamic and kinetic factors, especially the factors controlling the stability and interactions of shear planes, the relationship with point defect structures, and the mechanism of shear plane formation. In addition, electrical properties of compounds containing shear planes are studied. Reference to these factors will be made in the discussion that follows.
(C.R. A. CATLOW) F. Koch, J. B. Cohen, Acta Crystallogr., Sect. B, 25, 275 (1969). A. K. Cheetham, B. E. F. Fender, R. I. Taylor, J . Phys., C, 4, 2160 (1971). C. R A. Catlow, B. E. F. Fender, J. Phys., C , 8 , 3267 (1975). B. T. M. Willis, Proc. Br. Ceram. Soc., I , 9 (1964). C. R. A. Catlow, Proc. London, SOC.,Ser. A , 353, 533 (1977). C. R. A. Catlow, in Non-Stoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, 1981. 7. For a general review of microscopic studies of shear-plane-containing oxides see L. A. Bursill, B. G. Hyde, Prog. Solid State Chem., 7, 177 (1972).
1. 2. 3. 4. 5. 6.
3.10.1.2.2 Structural Properties
Shear plane formation is confined to the rutile-structured oxides ( T i 0 2- x and VOz - x ) and Re03-based structures [WO, and MOO,-,I (although MOO, does not
136
3.10.1 Introduction 3.10.1.2 Nonstoichiometryand Shear Planes 3.10.1.2.2 Structural Properties
(a) (102) plane
(b) (103) plane
(c) (104) plane
Figure 1. Different shear plane orientations in the R e 0 3 structure. The diagram gives ideal (i.e., unrelaxed) shear plane structures (a) (102) plane, (b) (103) plane, and (c) (104)
plane.
have the ReO, structure, regions of the reduced oxide phase MOO,-, have structures based on shear planes in a R e 0 3 structured host). There is evidence for related extended defects in ternary oxides such as reduced SI-T~O,~. This discussion concentrates on the simpler binary oxides.
3.1 0.1 Introduction
3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.3 Stability
137
The first structural feature is the occurrence of several shear plane orientations within the same phase. Thus reduction of W 0 3 leads to initial formation of (102) shear planes (see Fig. la) at low deviations from stoichiometry. However, with increasing oxygen loss (i.e., increasing value of x in the nonstoichiometric W 0 3 - x phase), the plane changes first to the (103) orientation (Fig. lb) then to the (104) orientation (Fig. lc). Finally, at large values of x, the (100) plane is formed. Similar behavior is found for T i 0 2 - x , where change or swinging of the shear plane orientation from the (132) to the (121) orientation is observed with increasing x'. The origin of the phenomenon of swinging shear planes is related to a second feature of shear plane structural chemistry, i.e., the formation of orderedoarrays of planes in which the separation between the planes can be large-up to 100 A. This ordering can lead to homologous series of definite compounds, of which the most widely studied is Ti,02,- ', in which n can vary 4 to 17; each compound has a well-defined unit cell based on shear planes in the rutile structured host, whose separation increases with the value of n. Homologous series are also observed in the W 0 3 and MOO, phases: series of general formula W n 0 3 n - 2and MOO, are well characterized'. Evidence for the structural features described above comes from electron microscopy and diffraction experiments on the ordered shear plane structures. Thus the structures of Ti40, (the n = 4 member of the Ti,02,-' homologous ~ e r i e s show ) ~ the occurrence of extensive relaxation (ca. 0.3 8, away from the shear plane of lattice cations in sites neighboring the plane). These relaxations stabilize the extended defects, as argued below. (C. R. A. CATLOW) 1. R. J. D. Tilley, in Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M.
Thomas, eds., Royal Society of Chemistry, Cambridge, 1978, London, 1978. 2. A. Magneli, Acta Crystallogr., 6, 495 (1953). 3. M. Marezio, P. F. Dernier, D. B. McWhan, J. P. Reimika, J . Solid State Chem., 6, 213 (1973). 3.10.1.2.3 Stability
Why should shear planes form in preference to point defects in a limited range of nonstoichiometric oxides? What factors control the relative stabilities of point-and extended-defect structures? Insight comes from computationally based theoretical techniques, which provide accurate values of the energetics of defect formation and of the cohesive properties of perfect crystal structures. The reliability of these methods in quantitative studies of crystal and defect energetics is now established in oxide and halide crystals'. The present applications concern the calculation of the shear plane and point defect e n e r g i e ~ ~ which - ~ , favor the anion vacancy as the more stable point defect, in contrast to the cation interstitial models suggested earlier5. Table 1 gives the calculated change in lattice energy involved in eliminating an oxygen atom from TiOz and W 0 3 by the two modes of reduction. In both cases the shear plane mode is of lower energy in accordance with the observation of these structures in reduced Ti02 - x and w03-,. The calculations refer to an equilibrated structure i.e., one in which the lattice is allowed to relax about the shear plane until the minimum energy configuration obtains. Large cation relaxations about the shear planes are calculated in accordance with experimental diffraction data. The calculations show, however, that if the relaxation were suppressed, (i.e., if the cations were returned to the centers of their octahedra), the energies of the shear planes would be raised, with the result that these species would now be less energetically
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.1 0.1 Introduction
3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.3 Stability
137
The first structural feature is the occurrence of several shear plane orientations within the same phase. Thus reduction of W 0 3 leads to initial formation of (102) shear planes (see Fig. la) at low deviations from stoichiometry. However, with increasing oxygen loss (i.e., increasing value of x in the nonstoichiometric W 0 3 - x phase), the plane changes first to the (103) orientation (Fig. lb) then to the (104) orientation (Fig. lc). Finally, at large values of x, the (100) plane is formed. Similar behavior is found for T i 0 2 - x , where change or swinging of the shear plane orientation from the (132) to the (121) orientation is observed with increasing x'. The origin of the phenomenon of swinging shear planes is related to a second feature of shear plane structural chemistry, i.e., the formation of orderedoarrays of planes in which the separation between the planes can be large-up to 100 A. This ordering can lead to homologous series of definite compounds, of which the most widely studied is Ti,02,- ', in which n can vary 4 to 17; each compound has a well-defined unit cell based on shear planes in the rutile structured host, whose separation increases with the value of n. Homologous series are also observed in the W 0 3 and MOO, phases: series of general formula W n 0 3 n - 2and MOO, are well characterized'. Evidence for the structural features described above comes from electron microscopy and diffraction experiments on the ordered shear plane structures. Thus the structures of Ti40, (the n = 4 member of the Ti,02,-' homologous ~ e r i e s show ) ~ the occurrence of extensive relaxation (ca. 0.3 8, away from the shear plane of lattice cations in sites neighboring the plane). These relaxations stabilize the extended defects, as argued below. (C. R. A. CATLOW) 1. R. J. D. Tilley, in Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M.
Thomas, eds., Royal Society of Chemistry, Cambridge, 1978, London, 1978. 2. A. Magneli, Acta Crystallogr., 6, 495 (1953). 3. M. Marezio, P. F. Dernier, D. B. McWhan, J. P. Reimika, J . Solid State Chem., 6, 213 (1973). 3.10.1.2.3 Stability
Why should shear planes form in preference to point defects in a limited range of nonstoichiometric oxides? What factors control the relative stabilities of point-and extended-defect structures? Insight comes from computationally based theoretical techniques, which provide accurate values of the energetics of defect formation and of the cohesive properties of perfect crystal structures. The reliability of these methods in quantitative studies of crystal and defect energetics is now established in oxide and halide crystals'. The present applications concern the calculation of the shear plane and point defect e n e r g i e ~ ~ which - ~ , favor the anion vacancy as the more stable point defect, in contrast to the cation interstitial models suggested earlier5. Table 1 gives the calculated change in lattice energy involved in eliminating an oxygen atom from TiOz and W 0 3 by the two modes of reduction. In both cases the shear plane mode is of lower energy in accordance with the observation of these structures in reduced Ti02 - x and w03-,. The calculations refer to an equilibrated structure i.e., one in which the lattice is allowed to relax about the shear plane until the minimum energy configuration obtains. Large cation relaxations about the shear planes are calculated in accordance with experimental diffraction data. The calculations show, however, that if the relaxation were suppressed, (i.e., if the cations were returned to the centers of their octahedra), the energies of the shear planes would be raised, with the result that these species would now be less energetically
138
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.3 Stability TABLE 1. CHANGE IN LATTICE COHESIVE ENERGY (AE,) ON ELIMINATING OXYGEN IONSBY SHEAR PLANE AND POINT
DEFECT MECHANISMS
Crystal Mode of Reduction
TiO,
WO,
Point defect
94.30 92.40
130.72 128.59
Shear plane
-
I
't
2-
C
T
Y
b
-
(T,
0
I-
0 1
I
17
I
16
I
15
I
14
I
13
I
12
-log POI (atm)
I
II
I
10
I
I
9
8
Figure 1. Plot of logarithm of conductivity versus logarithm of oxygen partial pressure for TiOz-x. (After Ref. 3.)
favored than the point defects. Cation relaxation is thus essential for the stability of shear planes. Indeed, shear planes form only5 in compounds having high values of the static dielectric constant c0 (- 150 and 300 for TiOl and W 0 3 ,respectively). High values of c0 imply that cations may be displaced from the lattice sites by an electrical field; for such materials large cation displacements about the shear planes, which are electrically charged entities, are expected. Table 1 also shows that there will be an equilibrium between extended and point defects. It is assumed that the reduced cations present in the nonstoichiometric phase are localized on sites neighboring the shear planes. The following equilibrium between extended and point defects: (sp)
+ Ova,+ 2M,
(a)
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.3 Stability
139
~~
represents the dissociation of the shear planes (sp) into oxygen vacancies (Ovac)and reduced cations (Mr).The activity of the shear planes may be approximated as unity. so that, using a standard mass action formalism, the oxygen vacancy concentration (xo) is given by: xo
= 4- 1,’3 exp
4 6 8 1 0
I5
(=)
- AGE
20
30
40
Number of Octoherlro Between CS Planes (n!
(a1 0.0r
-3
-01
g
-0.2-
2.
e
c
-;”
-
-0.3-
-U
I!
-0.40.51
1 0
1
IS
1 2G 25
Number of Octahedra Bctwe.cn
I
30
I
40
CS Planes (nl
(b) Figure 2. Calculated shear plane interaction energies variation of the interaction energy with interplanar spacing for (102) shear planes in an R e 0 3 structured oxide. (2a) “Constant volume” conditions, in which only atomic coordinates are relaxed. (2b) “Constant pressure” conditions, where coordinate and lattice vector relaxations were allowed. (From Ref. 8.)
3.10.1 Introduction 3.10.1.2 Nonstoichiometry and Shear Planes 3.10.1.2.3 Stability
140
where AG: is the standard free energy of the dissociation. Neglecting configurational entropy terms, AGE may be equated to the difference, given in Table 1, between the energies calculated for point defect and shear plane modes of reduction. The resulting M, showing that point defects will exist in value for xo at 1000 K for TiOz-x is equilibrium with the shear planes; such a concentration could have a decisive effect on, e.g., the transport properties of the nonstoichiometric phase. Moreover, it follows from this simple statistical mechanical analysis that for values of the deviation from stoichiometry, X , that are less than xo, point defects alone will be present. That is, for oxides in which shear planes are observed, there will be compositions close to stoichiometry in which point defects predominate, and the extent of this range will depend inversely on the value of AGE. The existence of a near-stoichiometric region that is dominated by point defects is supported for Ti02 --x by electrical conductivity data6 (Fig. 1) in the form of plots of the 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0
(a) Rutile lattice
0 0 0 0 0 0 0 0 0 0
0 0 0
x......
0 0 0 0
0 0 0 0 0 x 0 0 . 0 0 0 0 0 0 0
(b)(llO)apb x indicate interstitial site
X . 0 0
2
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
(c) (121) shearplane
0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0
2
Figure 3. Schematic representation of relation of (011) APB to (121) shear plane. Only cations in the (100) projection of rutile are shown: circles, Ti4+ ions; crosses, interstitial sites where addition of metal ions may lead to formation of a shear plane.
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logarithm of the conductivity (a) vs the logarithm of the partial pressure PO, in equilibrium with the Ti02 --x phase. The linear variation of log o with log PO, observed at high PO,is interpreted in terms of an equilibrium between the gas phase and a solid containing point defects. The proposition of shear plane point defect equilibria remains, however, controversial. It is argued that point defects cannot exist in those phases when shear planes are present, but such arguments are contradicted by statistical mechanical results. The computationally based theory used to obtain the results summarized in Table 1 is also valuable for studying certain interactions between shear planes (viz., those that are responsible for the ordering of extended defects). Continuum elasticity theory', identifies interactions of the elastic strain fields around the shear planes as the dominant effect. These conclusions are confirmed and amplified by atomistic computer modelingg, which calculates the interaction between shear planes [see Fig. 2 for the (102) shear plane in WO3 -J.There is interaction between these defects over large separations. It is such interactions that are responsible for the shear plane ordering. This is an illustration of the complexity of the problems that can now be handled by atomistic computer modeling. The kinetics reflect the three mechanisms of shear plane nucleation and growth: 1. Nucleation of a vacancy disk, followed by collapse with shear'. This mechanism is implied by the discussion of shear plane formation. 2. Nucleation of metal interstitials followed by rearrangement of the cation sublattice. This rearrangement mechanism is complex'0s 3. Attachment of metal interstitials to preexisting antiphase boundries (APBs)". "the mechanism summarized in Figure 3. Antiphase boundaries are conservative, planar defects; their formation involves creation in the cation sublattice of a fault that does not change the overall composition of the material. It is not clear which mechanism is operative, although calculations find no binding energies for small vacancy and interstitial nuclei. This favors mechanism 3 above. (C. R. A. CATLOW) 1. C. R. A. Catlow, J . Phys, C , 41, (1980). 2. C. R. A. Catlow, R. James, Nature, 272, 602 (1978). 3. R. James, Ph.D. thesis, University of London, 1979. 4. C. R. A. Catlow, R. James, Chern. Phys. Solids Their SurJ, 8, 108 (1980). 5. R. J. D. Tilley, Nature, 269, 229 (1977). 6. J. F. Baumard, D. Panis, A. M. Anthony, J . Solid State Chem., 20, 43 (1977). 7. A. M. Stoneham, P. J. Durham, J . Phys. Chem. Solids, 34, 2127 (1973). 8. E. Iguchi, R. J. D. Tilley, Philos. Trans. 286, 55 (1977). 9. A. N. Cormack, C. R. A. Catlow, P. W. Tasker, Radiat. Efl,74, 237 (1983). 10. J. S. Anderson, B. G. Hyde, J . Phys. Chern. Solids, 28, 1393 (1967). 11. C. R. A. Catlow, R. James, in Chemical Physics of Solids and Their Surfaces, M. W. Roberts, J. M. Thomas, eds., RSC Specialist Periodical Report No. 8, Royal Society of Chemistry, Cambridge, 1978. 12. L. A. Bursill, B. G. Hyde, M. O'Keeffe, Solid State Chemistry, R. S . Roth, S. J. Scheider, eds., NBS Special Publication No. 364, National Bureau of Standards, Washington, DC, 1972, p. 197.
3.10.1.3 Extended Defects 3.10.1.3.1 Crystallographic Shear
In a few transition metal oxides, changes in metal to oxygen ratio are accommodated by the formation of planar defects called crystallographic shear (CS) planes'-'. The
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.10.1 Introduction 3.10.1.3 Extended Defects 3.10.1.3.1 Crystallographic Shear
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logarithm of the conductivity (a) vs the logarithm of the partial pressure PO, in equilibrium with the Ti02 --x phase. The linear variation of log o with log PO, observed at high PO,is interpreted in terms of an equilibrium between the gas phase and a solid containing point defects. The proposition of shear plane point defect equilibria remains, however, controversial. It is argued that point defects cannot exist in those phases when shear planes are present, but such arguments are contradicted by statistical mechanical results. The computationally based theory used to obtain the results summarized in Table 1 is also valuable for studying certain interactions between shear planes (viz., those that are responsible for the ordering of extended defects). Continuum elasticity theory', identifies interactions of the elastic strain fields around the shear planes as the dominant effect. These conclusions are confirmed and amplified by atomistic computer modelingg, which calculates the interaction between shear planes [see Fig. 2 for the (102) shear plane in WO3 -J.There is interaction between these defects over large separations. It is such interactions that are responsible for the shear plane ordering. This is an illustration of the complexity of the problems that can now be handled by atomistic computer modeling. The kinetics reflect the three mechanisms of shear plane nucleation and growth: 1. Nucleation of a vacancy disk, followed by collapse with shear'. This mechanism is implied by the discussion of shear plane formation. 2. Nucleation of metal interstitials followed by rearrangement of the cation sublattice. This rearrangement mechanism is complex'0s 3. Attachment of metal interstitials to preexisting antiphase boundries (APBs)". "the mechanism summarized in Figure 3. Antiphase boundaries are conservative, planar defects; their formation involves creation in the cation sublattice of a fault that does not change the overall composition of the material. It is not clear which mechanism is operative, although calculations find no binding energies for small vacancy and interstitial nuclei. This favors mechanism 3 above. (C. R. A. CATLOW) 1. C. R. A. Catlow, J . Phys, C , 41, (1980). 2. C. R. A. Catlow, R. James, Nature, 272, 602 (1978). 3. R. James, Ph.D. thesis, University of London, 1979. 4. C. R. A. Catlow, R. James, Chern. Phys. Solids Their SurJ, 8, 108 (1980). 5. R. J. D. Tilley, Nature, 269, 229 (1977). 6. J. F. Baumard, D. Panis, A. M. Anthony, J . Solid State Chem., 20, 43 (1977). 7. A. M. Stoneham, P. J. Durham, J . Phys. Chem. Solids, 34, 2127 (1973). 8. E. Iguchi, R. J. D. Tilley, Philos. Trans. 286, 55 (1977). 9. A. N. Cormack, C. R. A. Catlow, P. W. Tasker, Radiat. Efl,74, 237 (1983). 10. J. S. Anderson, B. G. Hyde, J . Phys. Chern. Solids, 28, 1393 (1967). 11. C. R. A. Catlow, R. James, in Chemical Physics of Solids and Their Surfaces, M. W. Roberts, J. M. Thomas, eds., RSC Specialist Periodical Report No. 8, Royal Society of Chemistry, Cambridge, 1978. 12. L. A. Bursill, B. G. Hyde, M. O'Keeffe, Solid State Chemistry, R. S . Roth, S. J. Scheider, eds., NBS Special Publication No. 364, National Bureau of Standards, Washington, DC, 1972, p. 197.
3.10.1.3 Extended Defects 3.10.1.3.1 Crystallographic Shear
In a few transition metal oxides, changes in metal to oxygen ratio are accommodated by the formation of planar defects called crystallographic shear (CS) planes'-'. The
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oxides that support this way of accommodating stoichiometry changes are mainly WO,, MOO,, Nb205, T i 0 2 and V 0 2 . Crystallographic shear also occurs in some ternary compounds of these oxides (see 3.10.3). Apart from N b 2 0 5(see below), when these oxides are heated in an inert atmosphere or a vacuum so as to lose oxygen, or are heated in air with certain lower valent oxides (i.e., T i 0 2 , Cr2O3) the product consists of slabs of the parent structure joined along planar boundaries which are the CS planes. The relative positions of the two sheets of parent oxide across any one plane show that the original matrix has collapsed. With the oxides we are considering, this eliminates a plane of oxygen atoms, so that the product oxide has become slightly reduced compared to the parent oxide. In the CS plane, the octahedral coordination polyhedron around each cation is the same, except for minor distortions, as that in the parent structure. However, the linkage of these M 0 6 octahedra has been changed. In W 0 3 and Moo3, the change is from corner-sharing to edge-sharing, whereas in T i 0 2 and V 0 2 the change is from edge-sharing to face-sharing as shown in Figure 1, for W 0 3 and T i 0 2 . In all these materials, the indices of the CS plane vary, depending on the chemical conditions prevailing, i.e., the degree of reduction and the chemical nature of any lower valent doping ions involved in the reduction. Thus CS planes are usually characterized by the CS plane indices (hkl) and a displacement vector, the CS vector (uvw). The CS operation is symbolized as ( u c w ) (hkl). Since oxygen is eliminated in the process, and since the parent crystal collapses across the CS plane, the CS vector must have a component normal to the CS plane. See below (3.10.3)for details on the composition ranges over which CS occurs. Similar considerations apply to oxides related to Nb205 where two sets of almost mutually perpendicular CS planes occur at the same time, forming columns of parent
Figure 1. (a) Idealized drawing of (102)CS planes in reduced W 0 3 . The W 0 3 structure is represented as a corner-linking of W 0 6 octahedra (shaded squares in this projection). The CS plane contains blocks of four octahedra joined by edge-sharing. (b) Ball model drawing of a (121) CS plane in reduced T i 0 2 . The 02-anions are represented by large white spheres and the Ti4+ cations as small black spheres. In the CS plane there is a discontinuity and overlap of cation layers, which in a polyhedral model is revealed as a change from edge-sharing to face-sharing (Ti06) octahedra.
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structure instead of slabs. These are called “block structures” because the columns project as blocks in structural drawings (see 3.10.3). (R. J. D. TILLEY) 1. A. D. Wadsley, In Non-stoichiometric Compounds, L. Mandelcorn, ed., Academic Press, New York, 1962, p. 98. This reference is of considerable historical interest. 2. J. S. Anderson, in Surface and Defect Properties of Solids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 3. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids. Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 4. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 5. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 6. B. G. Hyde, A. N. Bagshaw, S. Andersson, M. O’Keeffe, Annu. Rev. Mater. Sci., 4, 43 (1974). 7. B. G. Hyde, S. Andersson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989.
3.10.1.3.2 Tunnel and Pentagonal Column Phases
Tunnel structures are commonly used by transition metals to accommodate nonstoi~hiometry’-~. In them, recognizable fragments of a parent structure are arranged to form an array of tunnels. This tunnel framework normally has a fixed composition; stoichiometric variability is introduced by filling the tunnels with a variable population of either metal atoms or metal cations plus oxygen. The most common tunnel cross sections encountered are hexagonal, pentagonal and square. Compounds containing hexagonal tunnels are exemplified by the hexagonal tungsten bronzes, MxW03, with M typically K and x typically from 0.2 to a maximum of 0.333 (Fig. 1). The composition of the framework is fixed at W 0 3 and the metal atoms partially or completely fill the hexagonal tunnels. They are prepared by electrolysis of
Figure 1. The idealized hexagonal tungsten bronze structure. Shaded squares represent WOs octahedra, which are corner-shared. This framework has a composition of W 0 3 . The inserted metal atoms (open circles in the tunnels) create the bronze MXWO3.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
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structure instead of slabs. These are called “block structures” because the columns project as blocks in structural drawings (see 3.10.3). (R. J. D. TILLEY) 1. A. D. Wadsley, In Non-stoichiometric Compounds, L. Mandelcorn, ed., Academic Press, New York, 1962, p. 98. This reference is of considerable historical interest. 2. J. S. Anderson, in Surface and Defect Properties of Solids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 3. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids. Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 4. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 5. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 6. B. G. Hyde, A. N. Bagshaw, S. Andersson, M. O’Keeffe, Annu. Rev. Mater. Sci., 4, 43 (1974). 7. B. G. Hyde, S. Andersson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989.
3.10.1.3.2 Tunnel and Pentagonal Column Phases
Tunnel structures are commonly used by transition metals to accommodate nonstoi~hiometry’-~. In them, recognizable fragments of a parent structure are arranged to form an array of tunnels. This tunnel framework normally has a fixed composition; stoichiometric variability is introduced by filling the tunnels with a variable population of either metal atoms or metal cations plus oxygen. The most common tunnel cross sections encountered are hexagonal, pentagonal and square. Compounds containing hexagonal tunnels are exemplified by the hexagonal tungsten bronzes, MxW03, with M typically K and x typically from 0.2 to a maximum of 0.333 (Fig. 1). The composition of the framework is fixed at W 0 3 and the metal atoms partially or completely fill the hexagonal tunnels. They are prepared by electrolysis of
Figure 1. The idealized hexagonal tungsten bronze structure. Shaded squares represent WOs octahedra, which are corner-shared. This framework has a composition of W 0 3 . The inserted metal atoms (open circles in the tunnels) create the bronze MXWO3.
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tungstate melts or by reaction of appropriate compositions of metal tungstate, WOJ and W metal in sealed SiOz tubes at about 1000-1400 K. Many metals that form hexagonal tungsten bronzes also form intergrowth tungsten bronze phases. The tunnel arrangement of the hexagonal structure is broken up into strips of single, double, or more complex tunnels, which are separated by regions of untransformed WOs-like structure (Fig. 2). In these, the nonstoichiometry is solely connected with the degree of tunnel filling but since the ratio of tunnel-like to nontunnel structures can vary, these compounds can extend over considerable composition ranges. In some phases (e.g., UMo5016 and U0.75M05014), the tunnels are partially or completely filled with 0-U-0 strings and are fully oxidized6. If the tunnel slabs are disordered or of variable width, an operationally nonstoichiometric disordered phase forms. However, they are often perfectly ordered and thus form homologous series of nonstoichiometric phases (see 3.10.1.4 and 3.10.3.3). Pentagonal tunnels typically occur in the tetragonal tungsten bronzes (Fig. 3), with a composition M,W03, typified by Pb,W03; x ranges between 0.18 and 0.35. The structure can be generated from that of WOs by rotating a block of four octahedra to create four pentagonal tunnels (Fig. 4). This rearrangement does not alter the matrix composition, and nonstoichiometric tungsten bronzes form as a result of a variable filling of the tunnels by metal atoms. In some cases, typically Na,W03, some of the square tunnels are filled.
Figure 2. Double strings of hexagonal tunnels coherently intergrown in a W03-type matrix. The tunnel strip may be regarded as a lamella of the hexagonal tungsten bronze structure.
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Figure 3. The tetragonal tungsten bronze structure: shaded squares, WOs octahedra; open circles, metal atoms in pentagonal tunnels, solid circles, metal atoms in square tunnels. In many tetragonal tungsten bronzes the square tunnels remain empty. If the pentagonal tunnels are filled with strings of metal cations plus oxide anions, the structure contains strings of M 0 7 pentagonal bipyramids linked by apical oxygen atoms. These features have been termed pentagonal columns or PCs4. Many fully oxidized tetragonal tungsten bronzes are known and can be represented by Nb'W9047. A wide range of ordered and disordered nonstoichiometric compounds can be created simply by distributing the units shown in Figure 4 throughout a W03-like matrix. The nonstoichiometry in the reduced bronzelike phases is due partly to the degree of tunnel filling and to the number of tunnels present. In the fully oxidized phases the tunnels are invariably full and the nonstoichiometry is due to the variable population of ordered or disordered PC units. New arrangements of these units distributed throughout a WO3like matrix are continually being reported7.The PC units can also be connected to form sheets (e.g., in the UOz-WO3 oxides)'. Disordered sheets of PCs generate operationally nonstoichiometric phases. Square tunnels occur in the tetragonal tungsten bronze structure and are sometimes filled by metal atoms. However, these tunnels are usually too small to accommodate many atoms, and larger square tunnels are necessary. Such tunnels typically characterize the hollandite structure. These materials are often derived from TiOz and can be generated theoretically from the rutile structure of Ti02 by rotation of strings of octahedra'. The tunnels are stabilized by large ions such as BaZCor, in the related forms
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Figure 4. Idealized drawing of four pentagonal tunnels coherently inserted into a W 0 3 type structure. Filling of these tunnels with M - 0 - M - 0 chains generates pentagonal columns, or PCs. of MnOz, by H20 or OH-. Hollandites, because they can enclose large cations, are being explored for use as storage matrices for radioactive waste. As with the other tunnel phases, the tunnel matrix is of fixed composition, and nonstoichiometry is due to variable filling of the tunnels by metal cations and oxygen anions. Partial or complete ordering of these species along the tunnels sometimes occur. These tunnel structures can intergrow with one element of the rutile structure to form a wide variety of nonstoichiometric phases analogous to the intergrowth tungsten bronzes (see 3.10.3.3). (R. J. D. TILLEY)
1. A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mandelcorn, ed., Academic Press, New York, 1963, p. 98. 2. B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O’Keeffe, Annu. Reu. Muter. Sci., 4, 43 (1974). 3. T. Ekstrom, R. J. D. Tilley, Chem. Scripta, 16, 1 (1980). 4. M. Lundberg, Chem. Comrnun., Uniu. Stockholm, No. XI1 (1971). 5. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 6. V. V. Tabachenko, 0. G. D’Yachenko, M. Sundberg, Eur. J . Solid State Inorg. Chem., 32, 1137 (1995). 7. F. Krumeich, G. Liedtke, W. Mader, Acta Crystallogr., Sect. B, 52, 917 (1996). 8. M. Sundberg, B.-0. Marinder, J . Solid State Chem., 121, 167 (1996). 3.10.13 . 3 Chemical Twinning and Related Structures
A twin plane is a planar boundary in a crystal, across which the two regions are related by reflection, or less frequently by glide and reflection or rotation’-’. If, however, there is no change of atom packing as one crosses a twin plane, no change in stoichiometry results. Thus, the a-PbO, structure may be regarded formally as multiply twinned rutile‘. In other cases, twin planes eliminate one cation or anion type or create at the twin plane unusual coordination polyhedra that are not found in the parent structure and can accommodate alternative cations to those found in the parent structure, Thus, the phases CazTiO4, BaNb206,and BaTi409 can all be regared as built from slabs of
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
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3.10.1 Introduction 3.10.1.3 Extended Defects 3.10.1.3.3 Chemical Twinning and Related Structures
Figure 4. Idealized drawing of four pentagonal tunnels coherently inserted into a W 0 3 type structure. Filling of these tunnels with M - 0 - M - 0 chains generates pentagonal columns, or PCs. of MnOz, by H20 or OH-. Hollandites, because they can enclose large cations, are being explored for use as storage matrices for radioactive waste. As with the other tunnel phases, the tunnel matrix is of fixed composition, and nonstoichiometry is due to variable filling of the tunnels by metal cations and oxygen anions. Partial or complete ordering of these species along the tunnels sometimes occur. These tunnel structures can intergrow with one element of the rutile structure to form a wide variety of nonstoichiometric phases analogous to the intergrowth tungsten bronzes (see 3.10.3.3). (R. J. D. TILLEY)
1. A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mandelcorn, ed., Academic Press, New York, 1963, p. 98. 2. B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O’Keeffe, Annu. Reu. Muter. Sci., 4, 43 (1974). 3. T. Ekstrom, R. J. D. Tilley, Chem. Scripta, 16, 1 (1980). 4. M. Lundberg, Chem. Comrnun., Uniu. Stockholm, No. XI1 (1971). 5. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 6. V. V. Tabachenko, 0. G. D’Yachenko, M. Sundberg, Eur. J . Solid State Inorg. Chem., 32, 1137 (1995). 7. F. Krumeich, G. Liedtke, W. Mader, Acta Crystallogr., Sect. B, 52, 917 (1996). 8. M. Sundberg, B.-0. Marinder, J . Solid State Chem., 121, 167 (1996). 3.10.13 . 3 Chemical Twinning and Related Structures
A twin plane is a planar boundary in a crystal, across which the two regions are related by reflection, or less frequently by glide and reflection or rotation’-’. If, however, there is no change of atom packing as one crosses a twin plane, no change in stoichiometry results. Thus, the a-PbO, structure may be regarded formally as multiply twinned rutile‘. In other cases, twin planes eliminate one cation or anion type or create at the twin plane unusual coordination polyhedra that are not found in the parent structure and can accommodate alternative cations to those found in the parent structure, Thus, the phases CazTiO4, BaNb206,and BaTi409 can all be regared as built from slabs of
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a NaCl structure type in twinned orientation, with the large cations accommodated in the channels lying between them. These are strictly stoichiometric compounds. Non stoichiometric oxides with repeated twinned structures are typified by some oxides of B, Mo, and W. The Mo4011 (orthorhombic) is made up of twinned slabs of an Re03-like M o o 3 structure united along (211) twin planes and linked by M o o 4 tetrahedra (Fig. 1). There are six MOOG octahedra in each slab, and the structure is the n = 6 member of the homologous series M n + 2 0 3 n + 4The . n = 7 phase, M o ~ . ~ W ~is ,also ~ Oknown6,’. ~ ~ , In these, the crystals are invariably disordered, with a variety of spacing and orientation mistakes in the twin planes producing non stoichiometric materials. Many structures with the same basic twinning motif are formed when W 0 3 reacts with the acidic PO4 group (Fig. 1)8. These materials, of formula P408(W03)2n,are referred to as “phosphate bronzes” and designated as (MPTB)p.The PO4 groups link the W03-like slabs, and the structures are identical to the molybdenum oxides above except that a wider range of n values occurs. As usual, there is considerable disorder in the twin plane spacing, generating nonstoichiometric compounds. There are two other series of related phosphate bronzes, again formed by a linkage of slabs of W03-like structure by way of PO4 groups. In these the planar faults at the slab boundaries are not twin planes. In the first, which have the designation (MPTB)H,the slabs are in parallel orientation rather than twinned. They are of the same structure as M o 4 0 1 (monoclinic). Apart from this molybdenum oxide, these phases have been formed only in the presence of alkali metals; thus the series formula is AxP408(W03)2n where A is typically Na or K. As prepared, these phases have a double source of nonstoichiometry, the disordered extended defects and the variable filling of the tunnels
Figure 1. Idealized structure of the (MPTB)p phases P 4 0 8 ( W 0 3 ) 2 nwith n = 6: diamonds, WO,(MoO,) octahedra; shaded triangles, PO,(MoO,) groups. Note that this structure is identical to that of M o 4 0 1 (orthorhombic).
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3.10.1 Introduction 3.10.1.3 Extended Defects 3.10.1.3.3 Chemical Twinning and Related Structures
Figure 2. Idealized crystal structure of the ludwigite configuration of (Mg, Mn)B05 showing the interleaved glide-twinned segments of rock salt structure: shaded diamonds, M 0 6 octahedra, solid triangles, B 0 3 groups. (see 10.3.1.3.2).In another series of nonstoichoimetric phosphate bronzes, (DPTB)H,the slabs of W0,-like structure are joined by P z 0 7groups. These structures have the same series formula as above, AxP408(W03)2n. The crystals are usually nonstoichiometric as a result of slab width variation and variable alkali metal content. The (Mg, Mn)B05 oxyborates, related to the minerals ludwigite and pinakiolite, are a series of nonstoichiometric compounds that contain twin planes as the dominant motif. These contain slabs of a rock salt structure type united by B 0 3 groups. The slabs are often in a glide-twinned relationship to each other and apart from pinakiolite, are interleaved in complex fashion (Fig. 2). Phases of these products often consist of heavily faulted structures in which the glide-twinned planes are disordered throughout the rock salt-type matrix'. Several other planar faults can be utilized to change the stoichiometry of oxide crystals. In the TiOZ-GazO3 system, isolated lamellae of the /3-Ga203structure grow into the rutile matrix at low GazO3 c~ncentrations'~~. Similarly in the SrTi0,-SrO system, lamellae of a SrO type interleave the perovskite structure to accommodate excess SrO. Many other examples can be cited4; some are discussed in the sections below. (R. J. D. TILLEY)
1. B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O'Keeffe, Annu. Rev. Muter. Sci., 4, 43 (1974). 2. S. Anderson, B. G. Hyde, J . Solid State Chem., 9, 92 (1974). 3. Y. Takeuchi, Recent Prog. Natl. Sci. Jpn., 3, 153 (1978). 4. R. J. D. Tilley, in Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M. Thomas, eds., Royal Society of Chemistry, Cambridge, 1980, p. 121. 5. B. G. Hyde, S . Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 6 . L. Kihlborg, B.-0. Marinder, M. Sundberg, F. Portemer, 0. Ringaby, J . Solid State Chem., 111, 111 (1994). 7 . 0. G. DYachenko, V. V. Tabachenko, M. Sundberg, J . Solid State Chem., 119, 8 (1995). 8. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. Solid State Inorg. Chem., 28, 93 (1991), and references therein. 9. J. J. Cooper, R. J. D. Tilley, J . Solid State Chem., 97, 452 (1992).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.10.1 Introduction 149 3.10.1.4 Coherent lntergrowth 3.10.1.4.1 Homologous Series Formed by Ordered Extended Defects 3.10.1.4 Coherent lntergrowth 3.10.1 -4.1 Homologous Series Formed by Ordered Extended Defects
In 3.10.1.3.1 it was shown that each crystallographic shear (CS) plane lowers the ratio of oxygen to metal in the crystal, resulting in the effective reduction of the present structure. With high CS plane populations, the degree of reduction becomes substantial; if the planes are completely ordered with a perfectly regular spacing in a crystallographic sense, a new oxide phase has formed. If the spacing between CS planes in such a regular array is considered to change, the oxides so formed are members of a homologous series where each phase has precisely defined stoichiometry, represented by the formula M,O,,-, ( n = thickness of slabs of parent structure oxide measured in units of M 0 6 coordination octahedra; m = number of oxygen atoms eliminated by each CS plane in a parent oxide of formula Examples are the (Mo, W)n03n-l series, where n ranges from 8 to ca. 16, and the Ti,Oz,- series, where n ranges from 4 to 10. Further examples are given later (3.10.3.1). The foregoing description applies to any extended defect ordered arrangement, including tunnels or twin planes, provided they change the composition of the parent structure. Any ordered arrangement generates a possible homologous series of compounds describable by a series formula and with each member having a precisely defined stoichiometry; e.g., the hexagonal tungsten bronze structure intergrows in ribbons with the W 0 3 structure to produce an ordered series of intergrowth tungsten bronzes. In these, a double strip of tunnels occurs as the integrowth elements, and the cations are the larger alkali metals, K', Cs', Rb', and Tl'. Related integrowth bronze structures apparently form in the SnXWO3,PbXWO3,and BaXWO3systems5 (see also below: 3.10.3.3). Another example of intergrowth of defects described in 3.10.1.3 involves the pentagonal column (PC) elements. When these are distributed in an ordered fashion in an Re03-type matrix, we generate variations of the TTB structure6,e.g., the Nb4W7031and Nb8W904,phases. Many isomorphous compounds are formed by replacement of Nb or W with other similar-sized ions. In the Ta2O5 region of the W 0 3 . T a 2 0 5system, many phases form consisting of ordered arrangements of PC elements along with some octahedral units. These structures are related to the low temperature structure of Ta2O5, ( L - T ~ ~ Oand ~ ) it, would appear that in this region any composition yields an ordered structure4 (see 3.10.3.4.2). Coherent intergrowth is related to this concept in several ways: consider two oxides of a series, with the values of n differing by one e.g., Ti901 and TiloO19. At compositions intermediate between Ti901 and TiloOl9, the preparations could be biphasic with both oxides present; alternatively, new ordered phases could form consisting of ordered arrangements of slabs of width corresponding to Ti9Ol7 and Ti10019 coherently grown. Whereas this does not seem to happen in the CS phases cited, it does occur in the Sn,W03 bronzes, where crystals of composition between n = 5 and n = 6 occur with ordered arrays of slabs alternating between n = 5 and n = 6, generating a new phase of fixed stoichiometry. A more extreme example occurs in the perovskite-related oxides of the (Na, Ca), Nb,03,+z series. End members of the series are Ca2Nb207and NaCa7Nb5OI7.These consist of perovskite structure slabs cut parallel to (110). In Ca,Nb,O,, these slabs are four octahedra thick, whereas in NaCa4Nb5Ol7they are five octahedra thick; these materials correspond to series members n = 4 and n = 5, respectively. Preparations between these two compositions lead to large numbers of ordered phases in which n = 4
150
3.10.1 Introduction 3.10.1.4 Coherent lntergrowth 3.10.1.4.2 Disordered Extended Defects
and n = 5 units are arranged in regularly, to account for any gross stoichiometry. Formally these oxides are members of the same homologous series, but with n values between 4 and 5. For example, the phase NaCa24Nb25087 is built of a repeat unit of five n = 4 layers followed by one n = 5 layer and has an overall n value of 4.166. Many more examples of lamellar intergrowth could be ~ i t e d and ~ - other ~ examples are given later (3.10.3). (R. J. D. TILLEY)
1. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1 M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 2. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids, Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 3. R. J. D. Tilley, M T P International Reviews ofscience, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 4. R. J. D. Tilley, M T P International Reviews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 5. R. J. D. Tilley, Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M. Thomas, eds., Royal Society of Chemistry, London, 1980, p. 124. 6. T. Ekstrom, R. J. D. Tilley, Chem. Scripta, 16, l(1980). 7. B. G. Hyde; S. Andersson, Inorganic Crystal Structures, Wiley-Interscience, New York, (1989). 8. D. R. Veblen, in Reviews in Mineralogy, Vol. 27, P. R. Buseck, ed., Mineral Society of America, Washington, D. C., 1992, Chap. 6. 3.10.1.4.2 Disordered Extended Defects
The ordering of the defects described in 3.10.1.3 takes place surprisingly often, particularly at high degrees of nonstoichiometry. With small changes in composition, such regular ordering is not usually found, and the result is a nonstoichiometric phase. Thus, in the CS-producing oxides W 0 3 and T i 0 2 , slight reduction generates disordered CS planes that appear to be arranged randomly throughout the matrix of the parent crystal. Slight oxidation or reduction of the Nb205-relatedblock structures also leads to the insertion of “wrong blocks”, which are coherently intergrown in the parent matrix, sometimes as random columns, but more often as lathes of new block structures that are inserted randomly or in a disordered way into the host crystal. These slightly reduced or oxidized phases are analogues of dilute point defect systems, but the defects are extended defects, such as CS planes. With V 0 2 , reduction leads to a two-phase product of unchanged V 0 2 and V 9 O I 7or V8OI5,containing ordered (121) CS planes. The disordered microstructues found when some systems are slightly reduced might represent the nonequilibrium nature of the products or indicate that the reaction has not truly gone to completion. There are other ways in which extended defects can disorder to give an operationally nonstoichiometric phase. Planar faults can be arranged almost randomly, even in appreciably reduced phases. A sample compositionally close to V 6 0 1 when quenched from the melt, has a microstructure of a disordered array of (121) CS planes. This corresponding to a disordered intergrowth of the phases V 4 0 7 , V 5 0 9 , V6OI1,V7OI3, V8OI5yielding an overall composition close to that prepared, although on a point-topoint basis there is significant compositional variation. This applies to almost all phases containing extended defects discussed here and, again, these microstructures are likely to correspond to nonequilibrium situations, The random intergrowth of extended defects occurs in the tunnel and PC phases. In short time preparations in the Ta2O5-WO3 system, an extensive TTB phase region
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 150
3.10.1 Introduction 3.10.1.4 Coherent lntergrowth 3.10.1.4.2 Disordered Extended Defects
and n = 5 units are arranged in regularly, to account for any gross stoichiometry. Formally these oxides are members of the same homologous series, but with n values between 4 and 5. For example, the phase NaCa24Nb25087 is built of a repeat unit of five n = 4 layers followed by one n = 5 layer and has an overall n value of 4.166. Many more examples of lamellar intergrowth could be ~ i t e d and ~ - other ~ examples are given later (3.10.3). (R. J. D. TILLEY)
1. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1 M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 2. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids, Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 3. R. J. D. Tilley, M T P International Reviews ofscience, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 4. R. J. D. Tilley, M T P International Reviews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 5. R. J. D. Tilley, Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M. Thomas, eds., Royal Society of Chemistry, London, 1980, p. 124. 6. T. Ekstrom, R. J. D. Tilley, Chem. Scripta, 16, l(1980). 7. B. G. Hyde; S. Andersson, Inorganic Crystal Structures, Wiley-Interscience, New York, (1989). 8. D. R. Veblen, in Reviews in Mineralogy, Vol. 27, P. R. Buseck, ed., Mineral Society of America, Washington, D. C., 1992, Chap. 6. 3.10.1.4.2 Disordered Extended Defects
The ordering of the defects described in 3.10.1.3 takes place surprisingly often, particularly at high degrees of nonstoichiometry. With small changes in composition, such regular ordering is not usually found, and the result is a nonstoichiometric phase. Thus, in the CS-producing oxides W 0 3 and T i 0 2 , slight reduction generates disordered CS planes that appear to be arranged randomly throughout the matrix of the parent crystal. Slight oxidation or reduction of the Nb205-relatedblock structures also leads to the insertion of “wrong blocks”, which are coherently intergrown in the parent matrix, sometimes as random columns, but more often as lathes of new block structures that are inserted randomly or in a disordered way into the host crystal. These slightly reduced or oxidized phases are analogues of dilute point defect systems, but the defects are extended defects, such as CS planes. With V 0 2 , reduction leads to a two-phase product of unchanged V 0 2 and V 9 O I 7or V8OI5,containing ordered (121) CS planes. The disordered microstructues found when some systems are slightly reduced might represent the nonequilibrium nature of the products or indicate that the reaction has not truly gone to completion. There are other ways in which extended defects can disorder to give an operationally nonstoichiometric phase. Planar faults can be arranged almost randomly, even in appreciably reduced phases. A sample compositionally close to V 6 0 1 when quenched from the melt, has a microstructure of a disordered array of (121) CS planes. This corresponding to a disordered intergrowth of the phases V 4 0 7 , V 5 0 9 , V6OI1,V7OI3, V8OI5yielding an overall composition close to that prepared, although on a point-topoint basis there is significant compositional variation. This applies to almost all phases containing extended defects discussed here and, again, these microstructures are likely to correspond to nonequilibrium situations, The random intergrowth of extended defects occurs in the tunnel and PC phases. In short time preparations in the Ta2O5-WO3 system, an extensive TTB phase region
3.10 Formation of Non-stoichiometric Oxides 3.10.1 Introduction 3.10.1.5 Classification of Nonstoichiometric Oxides
151
occurs, spanning the 2 T a 2 0 5 .7 W 0 3 and 4Ta205. 9 W 0 3 regions. The microstructure of this phase region shows that disordered PC elements occur in the structure. The disorder is rarely total, and recognizable domains of ordered structure are usually present. The existence of boundary regions between domains causes imprecision in defining the composition of the material; as domain sizes vary. The effect in practical terms is to produce a nonstoichiometric phase. Finally, there are the perovskite-related oxides. Although many perovskites utilize point defects or point defect clusters to change stoichiometry, the phases that also include a K2NiF4 structure oxide in the system, such as SrTiO, and Sr2Ti04, will form structures with disordered extended defects between these compositions. Ordered phases can be made within this stoichiometry range, but this usually requires long heating times at high temperatures. In practice, disordered planar faults occur in these operationally nonstoichiometric phases. A similar situation occurs in the A2B207-AB03perovskiterelated phases. Many other examples could be cited'-'. Some will be found in the sections concerned with nonstoichiometric oxides and oxide superconductors. (R. J. D. TILLEY) 1. L. A. Bursill, B. G. Hyde, Prog. Solid State Chem., 7, 177 (1972). 2. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972 p. 1. 3. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids, Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974. 4. R. J. D. Tilley, in M T P International Reviews ofscience, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 5 . R. J. D. Tilley, in M T P International Reviebvs ofscience, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed.; Butterworths, London, 1975, p. 73. 6. B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O'Keeffe, Annu. Rev. Muter. Sci., 4 , 43 (1974). 7. R. J. D. Tilley, in Chemical Physics ofSolids and Their Surfaces, Vol. 8 , M. W. Roberts, J. M. Thomas, eds., Royal Society ofchemistry, London, 1980, p. 121. 8. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 9. D. R. Veblen, in Review's in Mineralogy, Vol. 27, P. R. Buseck, Mineral Society of America, Washington, D.C., 1992.
3.10.1.5 Classification of Nonstoichiometric Oxides
Nonstoichiometry in a metal oxide implies that the cation is present in more than one oxidation state. It is not, therefore, surprising that the phenomenon is largely restricted to compounds of the transition, lanthanide, and actinide elements. For genuine nonstoichiometry, the material should conform to both structural and thermodynamic definitions of behavior. The structural definition requires that the X-ray diffraction pattern reveal the presence of a single phase whose cell dimensions vary smoothly with composition. Thermodynamically, nonstoichiometric compounds are characterized by their bivariant behavior. Consider, e.g., the phase rule applied to a nonstoichiometric oxide, MO,, in equilibrium with gaseous O2 at a fixed temperature:
MO,&MO,-d
6 2
+ - 0 2
F=C-P+2 C=2,P=2
.'. F = 2
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10 Formation of Non-stoichiometric Oxides 3.10.1 Introduction 3.10.1.5 Classification of Nonstoichiometric Oxides
151
occurs, spanning the 2 T a 2 0 5 .7 W 0 3 and 4Ta205. 9 W 0 3 regions. The microstructure of this phase region shows that disordered PC elements occur in the structure. The disorder is rarely total, and recognizable domains of ordered structure are usually present. The existence of boundary regions between domains causes imprecision in defining the composition of the material; as domain sizes vary. The effect in practical terms is to produce a nonstoichiometric phase. Finally, there are the perovskite-related oxides. Although many perovskites utilize point defects or point defect clusters to change stoichiometry, the phases that also include a K2NiF4 structure oxide in the system, such as SrTiO, and Sr2Ti04, will form structures with disordered extended defects between these compositions. Ordered phases can be made within this stoichiometry range, but this usually requires long heating times at high temperatures. In practice, disordered planar faults occur in these operationally nonstoichiometric phases. A similar situation occurs in the A2B207-AB03perovskiterelated phases. Many other examples could be cited'-'. Some will be found in the sections concerned with nonstoichiometric oxides and oxide superconductors. (R. J. D. TILLEY) 1. L. A. Bursill, B. G. Hyde, Prog. Solid State Chem., 7, 177 (1972). 2. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972 p. 1. 3. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids, Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974. 4. R. J. D. Tilley, in M T P International Reviews ofscience, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 5 . R. J. D. Tilley, in M T P International Reviebvs ofscience, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed.; Butterworths, London, 1975, p. 73. 6. B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O'Keeffe, Annu. Rev. Muter. Sci., 4 , 43 (1974). 7. R. J. D. Tilley, in Chemical Physics ofSolids and Their Surfaces, Vol. 8 , M. W. Roberts, J. M. Thomas, eds., Royal Society ofchemistry, London, 1980, p. 121. 8. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 9. D. R. Veblen, in Review's in Mineralogy, Vol. 27, P. R. Buseck, Mineral Society of America, Washington, D.C., 1992.
3.10.1.5 Classification of Nonstoichiometric Oxides
Nonstoichiometry in a metal oxide implies that the cation is present in more than one oxidation state. It is not, therefore, surprising that the phenomenon is largely restricted to compounds of the transition, lanthanide, and actinide elements. For genuine nonstoichiometry, the material should conform to both structural and thermodynamic definitions of behavior. The structural definition requires that the X-ray diffraction pattern reveal the presence of a single phase whose cell dimensions vary smoothly with composition. Thermodynamically, nonstoichiometric compounds are characterized by their bivariant behavior. Consider, e.g., the phase rule applied to a nonstoichiometric oxide, MO,, in equilibrium with gaseous O2 at a fixed temperature:
MO,&MO,-d
6 2
+ - 0 2
F=C-P+2 C=2,P=2
.'. F = 2
152
3.10.1 Introduction 3.10.1.5 Classification of Nonstoichiometric Oxides 3.10.15 . 1 Oxide Phases with Narrow Composition Ranges
There are two degrees of freedom i.e., bivariant behavior, so that at a fixed temperature the partial pressure of O2 is still a continuous function of composition. On the other hand, for two stoichiometric oxides, MO, and MO,, in equilibrium, we have MO,eMO,
n-m 2
+-
C=2,P=3
0 2
.'.F=l
Since there is now only one degree of freedom, at a fixed temperature, the partial pressure of O2 is constant, whatever the proportion of the two phases. It will be seen that problems arise in the application of both these definitions'.2. It is convenient to distinguish between nonstoichiometric materials with narrow composition ranges, < 0.1 mol %, and those that are grossly nonstoichiometric, although the distinction is arbitrary. The composition range often varies dramatically with temperature. The discussion will also embrace systems that form families of closely related line phases with unusual, albeit well-defined compositions. In much of the earlier literature, these families of ordered phases were mistakenly characterized as being nonstoichiometric. (A. K. CHEETHAM, R. J. D. TILLEY)
1. A. K. Cheetham, in Nonstoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, 1981. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publications, New York, 1995. 3.10.1 S.1 Oxide Phases with Narrow Composition Ranges
Many metal oxides exhibit nonstoichiometry at a level of < 0.1 mol% that is not readily detected by diffraction or thermodynamic methods. The change of composition may be undetectable over a wide range of Po, except from variations in the charge carrier concentration and, consequently, the electronic conductivity. Typical examples are given in Table 1'. The defects will typically be present as simple point defects-metal or oxygen vacancies or interstitials-and a treatment on this basis accounts for the observed properties such as the pressure dependence of electronic conductivity. When the TABLE1. HOMOGENEITY RANGES( x = O/M RATIO)OF SOMECOMMON METALOXIDES' Range
Ti,O, coo NiO cuzo NbO
1.501 1.000 1.000
0.5000 0.982
1.512 1.012 1.001 0.5016 1.008
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
152
3.10.1 Introduction 3.10.1.5 Classification of Nonstoichiometric Oxides 3.10.15 . 1 Oxide Phases with Narrow Composition Ranges
There are two degrees of freedom i.e., bivariant behavior, so that at a fixed temperature the partial pressure of O2 is still a continuous function of composition. On the other hand, for two stoichiometric oxides, MO, and MO,, in equilibrium, we have MO,eMO,
n-m 2
+-
C=2,P=3
0 2
.'.F=l
Since there is now only one degree of freedom, at a fixed temperature, the partial pressure of O2 is constant, whatever the proportion of the two phases. It will be seen that problems arise in the application of both these definitions'.2. It is convenient to distinguish between nonstoichiometric materials with narrow composition ranges, < 0.1 mol %, and those that are grossly nonstoichiometric, although the distinction is arbitrary. The composition range often varies dramatically with temperature. The discussion will also embrace systems that form families of closely related line phases with unusual, albeit well-defined compositions. In much of the earlier literature, these families of ordered phases were mistakenly characterized as being nonstoichiometric. (A. K. CHEETHAM, R. J. D. TILLEY)
1. A. K. Cheetham, in Nonstoichiometric Oxides, 0. T. Sorensen, ed., Academic Press, New York, 1981. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publications, New York, 1995. 3.10.1 S.1 Oxide Phases with Narrow Composition Ranges
Many metal oxides exhibit nonstoichiometry at a level of < 0.1 mol% that is not readily detected by diffraction or thermodynamic methods. The change of composition may be undetectable over a wide range of Po, except from variations in the charge carrier concentration and, consequently, the electronic conductivity. Typical examples are given in Table 1'. The defects will typically be present as simple point defects-metal or oxygen vacancies or interstitials-and a treatment on this basis accounts for the observed properties such as the pressure dependence of electronic conductivity. When the TABLE1. HOMOGENEITY RANGES( x = O/M RATIO)OF SOMECOMMON METALOXIDES' Range
Ti,O, coo NiO cuzo NbO
1.501 1.000 1.000
0.5000 0.982
1.512 1.012 1.001 0.5016 1.008
3.10.1 Introduction 3.10.1.5 Classification of NonstoichiometricOxides 3.10.1 5.2 Grossly Nonstoichiometric Phases
153
concentration of defects becomes higher, however, it is no longer possible to ignore the interactions between them. (A. K. CHEETHAM, R. J. D. TILLEY)
1. T. B. Reed, in The Chemistry ofExtended Defects in Non-Metallic Solids, L. Eyring, M. O’Keefe, eds., North-Holland, Amsterdam, 1970, p. 21. 3.10.1.5.2 Grossly Nonstoichiometric Phases
For a compound with a large range of nonstoichiometry standard thermodynamic or diffraction methods can be used to establish the compositional limits. In accordance with their disordered nature, these materials will adopt high symmetry structures and show a range of homogeneity that increases with increasing temperature”2. Some classical examples are listed in Table 1. High concentrations of defects are stabilized by defect interactions leading to the formation of clusters. Evidence for cluster formation is often indirect, since although the basic defect type (e.g., cation interstitials or oxygen vacancies) can be characterized by diffraction methods, the actual distribution of defects is more difficult to elucidate. Some of the evidence for cluster formation in Fe, -,O and U 0 2 + xis presented later (3.10.2.2). The preparation of a nonstoichiometric oxide of well-defined composition can be accomplished by standard high temperature methods, e.g., the iron(I1) oxide Feo.920can be prepared either by equilibrating Fe Fe2O3 at a suitable temperature (eg., 800°C) under the appropriate partial pressure of 02,or, more straightforwardly, by heating the correct proportions of Fe + F e 2 0 3 in a sealed quartz tube. In either case, it will be necessary to quench the sample to avoid disproportionation of the product into Fe Fe304. The exact specification of the factors that facilitate the formation of a grossly nonstoichiometric phase is not straightforward, but for ionic compounds, two criteria need to be met:
+
+
1. The metallic element must exist in more than one oxidation state, (e.g., Fe2+ and Fe3+). 2. The radii of the two cations must be similar. It is simple on this basis to appreciate why NiO and ZnO have narrow composition ranges: Ni(I1) and Zn(I1) are the most stable oxidation states of Ni and Zn, respectively. TABLE1. HOMOGENEITY RANGES (x = O/M RATIO)OF SOMEGROSSLY NOKSTOICHIOMETRIC COMPUNDS Range Oxide
&in
Ti0
0.80 0.75 1.000 1.042 1.75 2.00
vo
MnO FeO Pro2
uo2
Temperature (K) 1.39 1.30 1.073 1.163 2.00 2.20
1673 1573 1573 1373 1273 1673
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.1 Introduction 3.10.1.5 Classification of NonstoichiometricOxides 3.10.1 5.2 Grossly Nonstoichiometric Phases
153
concentration of defects becomes higher, however, it is no longer possible to ignore the interactions between them. (A. K. CHEETHAM, R. J. D. TILLEY)
1. T. B. Reed, in The Chemistry ofExtended Defects in Non-Metallic Solids, L. Eyring, M. O’Keefe, eds., North-Holland, Amsterdam, 1970, p. 21. 3.10.1.5.2 Grossly Nonstoichiometric Phases
For a compound with a large range of nonstoichiometry standard thermodynamic or diffraction methods can be used to establish the compositional limits. In accordance with their disordered nature, these materials will adopt high symmetry structures and show a range of homogeneity that increases with increasing temperature”2. Some classical examples are listed in Table 1. High concentrations of defects are stabilized by defect interactions leading to the formation of clusters. Evidence for cluster formation is often indirect, since although the basic defect type (e.g., cation interstitials or oxygen vacancies) can be characterized by diffraction methods, the actual distribution of defects is more difficult to elucidate. Some of the evidence for cluster formation in Fe, -,O and U 0 2 + xis presented later (3.10.2.2). The preparation of a nonstoichiometric oxide of well-defined composition can be accomplished by standard high temperature methods, e.g., the iron(I1) oxide Feo.920can be prepared either by equilibrating Fe Fe2O3 at a suitable temperature (eg., 800°C) under the appropriate partial pressure of 02,or, more straightforwardly, by heating the correct proportions of Fe + F e 2 0 3 in a sealed quartz tube. In either case, it will be necessary to quench the sample to avoid disproportionation of the product into Fe Fe304. The exact specification of the factors that facilitate the formation of a grossly nonstoichiometric phase is not straightforward, but for ionic compounds, two criteria need to be met:
+
+
1. The metallic element must exist in more than one oxidation state, (e.g., Fe2+ and Fe3+). 2. The radii of the two cations must be similar. It is simple on this basis to appreciate why NiO and ZnO have narrow composition ranges: Ni(I1) and Zn(I1) are the most stable oxidation states of Ni and Zn, respectively. TABLE1. HOMOGENEITY RANGES (x = O/M RATIO)OF SOMEGROSSLY NOKSTOICHIOMETRIC COMPUNDS Range Oxide
&in
Ti0
0.80 0.75 1.000 1.042 1.75 2.00
vo
MnO FeO Pro2
uo2
Temperature (K) 1.39 1.30 1.073 1.163 2.00 2.20
1673 1573 1573 1373 1273 1673
154
3.10.1 Introduction 3.1 0.1.5 Classification of NonstoichiometricOxides 3.10.15.3 Homologous Series of Metal Oxides
Similarly, the narrow range of COOcompared with FeOopresumablystems from the larFe difference between the radii of high spin d7 Co2+(0.74 A) and low spin d6 Co3+ (0.53 A); both the cations in FeO are high spin with radii of 0.78 8, (Fe2+)and 0.65 8, (Fe3+), respectively. However, our two criteria are clearly not sufficient conditions-Fe203, e.g., is a line phase-and it would appear that some structures such as fluorite and rock salt are more prone to nonstoichiometry than others. (A. K. CHEETHAM, R. J. D. TILLEY) 1. M. D. Banus, T. B. Reed, in T h e Chemistry of Extended Defects in Non-Metallic Solids, L. Eyring, M . OKeefe, eds., North-Holland, Amsterdam, 1970, p. 488. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York. 1995. 3.10.15 3 Homologous Series of Metal Oxides
The occurrence of oxide phases with obscure but well-defined compositions can arise in several ways. Section 3.10.1.3describes how the reduction of, e.g., MOO, leads to a homologous series of ordered phases ( n and m are integers) by the formation of crystallographic shear (CS) planes. Systems that exhibit similar behavior are T i 0 2 , VOz, CrOz, N b 2 0 5 ,and W 0 3 ' . This mechanism is favored by the high valence cations at the beginning of the transition series because it permits the cation to retain octahedral coordination rather than lower the coordination number by the creation of oxygen vacancies (the disruption of the cation sublattice is less favored for higher oxides on electrostatic grounds). In the reduced TiOz system, there are two series of phases, both with the general formula Ti,02,-1. In the composition range Ti01,75to TiO1.90, members with n = 4 to 10 have a CS plane orientation of {121}Tio2,and between TiO1.94 and Ti02,00,there is a series with 15 < n < 36 and {132}Ti02C s An entirely different class of ordered phases is found in the P r - 0 system. Whereas at temperatures exceeding ca. 873 K, P r o z - - x is genuinely nonstoichiometric, the defect interactions lead to the formation of a homologous series of phases Pr,OZ,- (n = 7, 9, 10,11,12)as the oxygen vacancies become ordered at lower temperatures4. This behavior underlines the delicate balance that can exist between ordered and disorder states. See below (3.10.2.2.2)for more detail. A characteristic of the ordered phases found in the shear plane systems and P r o z - x is that they are line phases with two-phase regions extending between adjacent members of each series. One exception to this rule is found in the Ti02-Cr203 system, which, like T i 0 2 - x , exhibits two sets of shear phases with {121}Tio2and {132jTiO2 CS plane orientations, respectively (see above). In the intervening composition range, MO1.90M01.94,the CS planes rotate continuously from {lzl} to {132}, traversing every intermediate orientation in the {111)Ti02zone5. In this way, a continuum of unique ordered phases is generated-a series of so-called infinitely adaptive structures. This theme is discussed further below (3.10.1.6.5). (A. K. CHEETHAM, R. J. D. TILLEY) 1. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 5. 2. S. Anderson, A. Magneli, Natur~~issenschaften, 43, 495 (1956). 3. L. A. Bursill, B. G. Hyde, Acta Crystallogr. Sect. B, 27, 210 (1971). 4. B. G. Hyde, D. J. M. Bevan, L. Eyring, Philos, Trans, R. Soc. London, Ser. A , 259, 583 (1966). 5. L. A. Bursill, B. G. Hyde, D. K. Philp. Phil. ,May., 23, 1501 (1971).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 154
3.10.1 Introduction 3.1 0.1.5 Classification of NonstoichiometricOxides 3.10.15.3 Homologous Series of Metal Oxides
Similarly, the narrow range of COOcompared with FeOopresumablystems from the larFe difference between the radii of high spin d7 Co2+(0.74 A) and low spin d6 Co3+ (0.53 A); both the cations in FeO are high spin with radii of 0.78 8, (Fe2+)and 0.65 8, (Fe3+), respectively. However, our two criteria are clearly not sufficient conditions-Fe203, e.g., is a line phase-and it would appear that some structures such as fluorite and rock salt are more prone to nonstoichiometry than others. (A. K. CHEETHAM, R. J. D. TILLEY) 1. M. D. Banus, T. B. Reed, in T h e Chemistry of Extended Defects in Non-Metallic Solids, L. Eyring, M . OKeefe, eds., North-Holland, Amsterdam, 1970, p. 488. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York. 1995. 3.10.15 3 Homologous Series of Metal Oxides
The occurrence of oxide phases with obscure but well-defined compositions can arise in several ways. Section 3.10.1.3describes how the reduction of, e.g., MOO, leads to a homologous series of ordered phases ( n and m are integers) by the formation of crystallographic shear (CS) planes. Systems that exhibit similar behavior are T i 0 2 , VOz, CrOz, N b 2 0 5 ,and W 0 3 ' . This mechanism is favored by the high valence cations at the beginning of the transition series because it permits the cation to retain octahedral coordination rather than lower the coordination number by the creation of oxygen vacancies (the disruption of the cation sublattice is less favored for higher oxides on electrostatic grounds). In the reduced TiOz system, there are two series of phases, both with the general formula Ti,02,-1. In the composition range Ti01,75to TiO1.90, members with n = 4 to 10 have a CS plane orientation of {121}Tio2,and between TiO1.94 and Ti02,00,there is a series with 15 < n < 36 and {132}Ti02C s An entirely different class of ordered phases is found in the P r - 0 system. Whereas at temperatures exceeding ca. 873 K, P r o z - - x is genuinely nonstoichiometric, the defect interactions lead to the formation of a homologous series of phases Pr,OZ,- (n = 7, 9, 10,11,12)as the oxygen vacancies become ordered at lower temperatures4. This behavior underlines the delicate balance that can exist between ordered and disorder states. See below (3.10.2.2.2)for more detail. A characteristic of the ordered phases found in the shear plane systems and P r o z - x is that they are line phases with two-phase regions extending between adjacent members of each series. One exception to this rule is found in the Ti02-Cr203 system, which, like T i 0 2 - x , exhibits two sets of shear phases with {121}Tio2and {132jTiO2 CS plane orientations, respectively (see above). In the intervening composition range, MO1.90M01.94,the CS planes rotate continuously from {lzl} to {132}, traversing every intermediate orientation in the {111)Ti02zone5. In this way, a continuum of unique ordered phases is generated-a series of so-called infinitely adaptive structures. This theme is discussed further below (3.10.1.6.5). (A. K. CHEETHAM, R. J. D. TILLEY) 1. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 5. 2. S. Anderson, A. Magneli, Natur~~issenschaften, 43, 495 (1956). 3. L. A. Bursill, B. G. Hyde, Acta Crystallogr. Sect. B, 27, 210 (1971). 4. B. G. Hyde, D. J. M. Bevan, L. Eyring, Philos, Trans, R. Soc. London, Ser. A , 259, 583 (1966). 5. L. A. Bursill, B. G. Hyde, D. K. Philp. Phil. ,May., 23, 1501 (1971).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.1 Introduction 3.10.1.5 Classification of Nonstoichiometric Oxides 3.10.15 . 5 Oxides with Modulated Structures
155
3.10.1 S.4 Coherently lntergrown Structures
Although it can be stated that the regions between adjacent phases in the shear structure and P r o 2 -x-type systems are truly biphasic, characterization of these regions is often difficult. Members of a given series of phases have a close structural relationship and are frequently able to intergrow coherently with one another. Rather than containing discrete particles of two adjacent phases, samples of intermediate composition may contain inhomogeneous crystallites incorporating domains of each phase. Under these circumstances, an additional variable-the interface energy, which will be sample-dependent-is required to define the free energy of the system. The number of degrees of freedom is thereby increased and, for such a material, bivariant rather than univariant thermodynamic behavior will be observed's2. To distinguish between random, coherent intergrowth and classical nonstoichiometry, it is necessary to probe with diffraction methods. Powder X-ray patterns will normally be diffuse and uninformative, but high resolution electron microscopy, which has played a vital role in the elucidation of CS-type structures, will often reveal the true state of affairs. This behavior is nicely illustrated by an electron optical study of the SrO-TiO, system3. The end members Sr2Ti04(K2NiF4structure) and SrTi03 (perovskite structure) could, in principle, intergrow to form a homologous series Sr,, 'Ti,03,+ 1, and the phases Sr3Ti206 and Sr4Ti3010have been reported from X-ray studies. An electron optical examination of the system reveals, only phases Sr2Ti04, Sr3Ti207,and SrTiO,, as discrete compounds, but micrographs of samples with compositions intermediate between Sr3Ti207 and SrTiO, show a considerable mutual solubility, with lamellae of each plane coherently intergrown into crystals of the other. It could be argued that these intergrowths are genuine nonstoichiometric phases, but based on planar, rather than point, defects. The seemingly random coherent intergrowth found in the Sr-Ti-0 system provides an interesting contrast with the behavior found in the barium ferrites in the composition range between BaFeI2Ol9and Ba2Me2Fe12022 (Me = Ni, Co, Zn). Here, the ability of the end members to intergrow not only coherently, but also regularly, leads to a continuum of ordered phases4. Ordered, coherent intergrowth is also known in the niobium oxide "block" structures: e.g., the structure of W 4 N b 2 6 0 7 7corresponds to an ordered intergrowth of the phases W N b 1 2 0 3 3and W3Nb140445.In this case, however, there is no suggestion of a continuum of such intergrowth phases. (A. K. CHEETHAM, R. J. D. TILLEY) 1. R. R. Merritt, B. G. Hyde, L. A. Bursill, D. K. Philp, Philos. Trans. R. Sot. London, Ser. A , 274,627
(1973).
2. C. N. R. Rao, B. Raveau; Transition Metal Oxides, VCH Publishers, New York, 1995. 3. R. J. D. Tilley, J . Solid State Chem., 21, 293 (1977). 4. R. J. D. Tilley, in Surface and Defect Properties ofSolids,Vol. 8, M. W. Roberts,J. M. Thomas eds., Specialist Periodical Reports Chemical Society, London, 1980, p. 121. 5. A. D. Wadsley, S. Anderson, Perspect. Struct. Chern., 3 , 1 (1970). 3.10.1 5 . 5 Oxides with Modulated Structures
There exist systems in which the structure can adapt uniquely, over a range of composition, to any particular stoichiometry. These compounds are known as infinitely adaptive (modulated) structures'. Every composition becomes ordered into a superstructure that is characteristic of that composition only, so that an apparent continuum of closely spaced structures is generated without intervening two-phase regions. A system of
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.1 Introduction 3.10.1.5 Classification of Nonstoichiometric Oxides 3.10.15 . 5 Oxides with Modulated Structures
155
3.10.1 S.4 Coherently lntergrown Structures
Although it can be stated that the regions between adjacent phases in the shear structure and P r o 2 -x-type systems are truly biphasic, characterization of these regions is often difficult. Members of a given series of phases have a close structural relationship and are frequently able to intergrow coherently with one another. Rather than containing discrete particles of two adjacent phases, samples of intermediate composition may contain inhomogeneous crystallites incorporating domains of each phase. Under these circumstances, an additional variable-the interface energy, which will be sample-dependent-is required to define the free energy of the system. The number of degrees of freedom is thereby increased and, for such a material, bivariant rather than univariant thermodynamic behavior will be observed's2. To distinguish between random, coherent intergrowth and classical nonstoichiometry, it is necessary to probe with diffraction methods. Powder X-ray patterns will normally be diffuse and uninformative, but high resolution electron microscopy, which has played a vital role in the elucidation of CS-type structures, will often reveal the true state of affairs. This behavior is nicely illustrated by an electron optical study of the SrO-TiO, system3. The end members Sr2Ti04(K2NiF4structure) and SrTi03 (perovskite structure) could, in principle, intergrow to form a homologous series Sr,, 'Ti,03,+ 1, and the phases Sr3Ti206 and Sr4Ti3010have been reported from X-ray studies. An electron optical examination of the system reveals, only phases Sr2Ti04, Sr3Ti207,and SrTiO,, as discrete compounds, but micrographs of samples with compositions intermediate between Sr3Ti207 and SrTiO, show a considerable mutual solubility, with lamellae of each plane coherently intergrown into crystals of the other. It could be argued that these intergrowths are genuine nonstoichiometric phases, but based on planar, rather than point, defects. The seemingly random coherent intergrowth found in the Sr-Ti-0 system provides an interesting contrast with the behavior found in the barium ferrites in the composition range between BaFeI2Ol9and Ba2Me2Fe12022 (Me = Ni, Co, Zn). Here, the ability of the end members to intergrow not only coherently, but also regularly, leads to a continuum of ordered phases4. Ordered, coherent intergrowth is also known in the niobium oxide "block" structures: e.g., the structure of W 4 N b 2 6 0 7 7corresponds to an ordered intergrowth of the phases W N b 1 2 0 3 3and W3Nb140445.In this case, however, there is no suggestion of a continuum of such intergrowth phases. (A. K. CHEETHAM, R. J. D. TILLEY) 1. R. R. Merritt, B. G. Hyde, L. A. Bursill, D. K. Philp, Philos. Trans. R. Sot. London, Ser. A , 274,627
(1973).
2. C. N. R. Rao, B. Raveau; Transition Metal Oxides, VCH Publishers, New York, 1995. 3. R. J. D. Tilley, J . Solid State Chem., 21, 293 (1977). 4. R. J. D. Tilley, in Surface and Defect Properties ofSolids,Vol. 8, M. W. Roberts,J. M. Thomas eds., Specialist Periodical Reports Chemical Society, London, 1980, p. 121. 5. A. D. Wadsley, S. Anderson, Perspect. Struct. Chern., 3 , 1 (1970). 3.10.1 5 . 5 Oxides with Modulated Structures
There exist systems in which the structure can adapt uniquely, over a range of composition, to any particular stoichiometry. These compounds are known as infinitely adaptive (modulated) structures'. Every composition becomes ordered into a superstructure that is characteristic of that composition only, so that an apparent continuum of closely spaced structures is generated without intervening two-phase regions. A system of
156
3.10.1 Introduction 3.10.1.5 Classification of NonstoichiometricOxides 3.10.15 . 5 Oxides with Modulated Structures
this type will exhibit pseudobivariant behavior and cannot be diagnosed by thermodynamic means. Our present knowledge in this area is, therefore, obtained by structural methods. For long-range order to be complete at essentially any composition, the periodicity of the structure may become extremely large in certain cases, with unit cell dimensions of hundreds of angstroms (1 A = 10 m). It is not necessary, nor indeed likely, that the interionic forces should operate over such large distances. An alternative rationalization that seems appropriate in some cases suggests a slight misfit between the periodicity of, e.g., the cation sublattice and that of the anions, so that they coincide only at regular, well-separated intervals. These structures are sometimes described as vernier structures, incommensurate phases, or modulated structures. The materials that exhibit this phenomenon include alloys, chalcogenides, oxofluorides, and oxides2, and some of the systems of relevance in the present section are T a z Oj-W03, Y(O/F),+,, and Ti02-Cr2032. One example of an infinitely adaptive structure, the rotating shear plane, was described earlier (3.10.1.5.3); see also the discussion of the coherently intergrown barium ferrite type (3.10.1.5.4). This section illustrates the behavior further with the example of Y(O/F), t x , a structure modulated by variations in the concentrations of the anions. The Y(O/F),,, system consists of an apparent continuum of structures in the composition range YX2.12to YX2.,, (X = 0 + F)3. The structures of three compounds in this continuum are known Y 5 0 4 F 7 ,Y6OjF8, and Y 7 0 6 F 9 , and each belongs to the homologous series Y,O,, (e.g., Y706F9)4. The cations are hardly displaced from the ideal fluorite sites, nor are the anions at x 0.5. The remaining anions, located at x 0, are more densely packed and coincide with the x 0.5 array every eighth fluorite subcell along y . The other members of the homologous series can be described in a similar manner. Intermediate phases have also been examined, e.g., Y17014F23, which can be described either as an intergrowth of 2(Y60jF8)+ Y504F7 or in terms of noncommensurate arrays. These continuous homologous series are difficult to handle from a crystallographic point of view since some reflections on diffraction patterns do not fall on the nodes of the conventional reciprocal lattice but at incommensurate positions with respect to the subcell. In the example just given, this would be the fluorite subcell. It has been recognized that many oxides fall into this category, and these compounds are now more corectly referred to as incommensurate structures or modulated structures5 although the term “infinitely adaptive” compounds retains some utility. Such structures are now described in terms of a subcell onto which is imposed a modulation wave that is incommensurate with the subcell. The modulation wave can describe the deviation of some of the atoms from the ideal positions in the subcell, a positionally modulated structure, or the variation in occupancy of some of the sites with respect to the ideal occupancy, a compositionally modulated structure. Crystallographic methods for dealing with such systems are now evolving6.For example, the oxide L - T ~ has ~ Oa complex ~ structure which is not readily described conventionally. T o a first approximation the Ta atoms form a uniform hexagonal array. The difficulty rests in describing the oxygen atom positions. These positions can be described by a wave related to an ordinary sine wave but more complex. The modulation wave is such that the positions of the oxygen atoms are a compromise between providing the pentagonalbipyramidal coordination demanded by the size of the large Ta atoms and the octahedral coordination needed to generate a T a z 0 5 stoichiometry. The modulation wave is a compromise between the needs for composition (i.e., valence) and crystal chemistry (i.e., coordination polyhedra). T o a reasonable approximation, a percentage of the Ta atoms
-
- -
157 3.10 Formation of Non-stoichiometric Oxides 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.1 Binary Oxides with Narrow Chemically Insignificant Composition Range
can be allocated to pentagonal-bipyramidal coordination and the rest to octahedral coordination; however, both polyhedra are in fact distorted. As the temperature increases, the modulation wave changes so as to increase the number of metal atoms in octahedral coordination at the expense of the pentagonal bipyramidally coordinated atoms. The modulation wave varies smoothly with temperature within the stability range of L-Ta2OS. L-Ta2OSitself can form “solid solutions” with a number of other oxides, including A1203, TiOz, W 0 3 and Zr02’. In terms of the adaptive compounds description, these composition ranges were described as comprising a closely spaced series of microphases. Better, they can be described as incommensurate or modulated structures. As the composition varies, the modulation wave has to compromise between the positions of the oxygen atoms, the composition, and the coordination preferences of the doped atoms while maintaining the metal atom array in a hexagonal arrangement. The resulting compromise is described by an oxygen atom modulation wave. This in turn modulates the position of the metal atoms in the hexagonal array slightly. For example, if the T a 2 0 5 is reacted with W 0 3 , the modulation wave changes from that in the pure oxide to accommodate more oxygen and more metal atoms (mainly W) in octahedral coordination. If ZrOz is the dopant, the wave must be such as to take into account less oxygen in the structure and more atoms in pentagonal-bipyramidal coordination. In the oxyfluorides cited above, the same phenomenon is found’. The composition range, originally described in terms of a succession of microphases, is now seen to be more accurately described as a continuum. The metal atoms occupy the normal fluorite positions, and the oxygen and fluorine positions are described in terms of a modulation wave that acts to balance the competing needs of composition and coordination preference of the atoms involved. As the composition changes, the modulation wave changes smoothly so as to always arrive at the best compromise. The number of such nonstoichiometric oxides (and other compounds) that can be described in this way is growing, the future work is likely to reveal that this aspect of inorganic chemistry gains in significance. (A. K. CHEETHAM, R. J. D. TILLEY) J. S. Anderson, J . Chem. Sot., Dalton Trans., 1107 (1973). R. S. Roth, Prog. Solid State Chem., 13, 159 (1980). A. W. Mann, D. J. M. Bevan, J . Solid State Chem., 5, 410 (1972). D. J. M. Bevan, A. W. Mann, Acta Crystallogr., Sect. B, 31, 1406 (1975). S. Van Smaalen, Crystallogr. Rev.,4, 79 (1995). T. Janssen, A. Janner, Adv. Phy., 36, 519 (1987). S. Schmid, J. G. Thompson, A. D. Rae, B. D. Butler, R. L. Withers, Acta Crystallogr., Sect. B, 51, 698 (1995); A. D. Rae, S. Schmid, J. G. Thompson, R. L. Withers, Acta Crystallogr., Sect. B, 51, 709 (1995). 8. S. Schmid, R. L. Withers, J. G. Thompson, J . Solid State Chem., 99, 226 (1992).
1. 2. 3. 4. 5. 6. 7.
3.1 0.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.1 Binary Oxides with Narrow Chemically Insignificant Composition Range
Compositions with extremely small deviations from stoichiometry can be prepared by heating stoichiometric compounds to high temperatures, by exposure to ionizing
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
157 3.10 Formation of Non-stoichiometric Oxides 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.1 Binary Oxides with Narrow Chemically Insignificant Composition Range
can be allocated to pentagonal-bipyramidal coordination and the rest to octahedral coordination; however, both polyhedra are in fact distorted. As the temperature increases, the modulation wave changes so as to increase the number of metal atoms in octahedral coordination at the expense of the pentagonal bipyramidally coordinated atoms. The modulation wave varies smoothly with temperature within the stability range of L-Ta2OS. L-Ta2OSitself can form “solid solutions” with a number of other oxides, including A1203, TiOz, W 0 3 and Zr02’. In terms of the adaptive compounds description, these composition ranges were described as comprising a closely spaced series of microphases. Better, they can be described as incommensurate or modulated structures. As the composition varies, the modulation wave has to compromise between the positions of the oxygen atoms, the composition, and the coordination preferences of the doped atoms while maintaining the metal atom array in a hexagonal arrangement. The resulting compromise is described by an oxygen atom modulation wave. This in turn modulates the position of the metal atoms in the hexagonal array slightly. For example, if the T a 2 0 5 is reacted with W 0 3 , the modulation wave changes from that in the pure oxide to accommodate more oxygen and more metal atoms (mainly W) in octahedral coordination. If ZrOz is the dopant, the wave must be such as to take into account less oxygen in the structure and more atoms in pentagonal-bipyramidal coordination. In the oxyfluorides cited above, the same phenomenon is found’. The composition range, originally described in terms of a succession of microphases, is now seen to be more accurately described as a continuum. The metal atoms occupy the normal fluorite positions, and the oxygen and fluorine positions are described in terms of a modulation wave that acts to balance the competing needs of composition and coordination preference of the atoms involved. As the composition changes, the modulation wave changes smoothly so as to always arrive at the best compromise. The number of such nonstoichiometric oxides (and other compounds) that can be described in this way is growing, the future work is likely to reveal that this aspect of inorganic chemistry gains in significance. (A. K. CHEETHAM, R. J. D. TILLEY) J. S. Anderson, J . Chem. Sot., Dalton Trans., 1107 (1973). R. S. Roth, Prog. Solid State Chem., 13, 159 (1980). A. W. Mann, D. J. M. Bevan, J . Solid State Chem., 5, 410 (1972). D. J. M. Bevan, A. W. Mann, Acta Crystallogr., Sect. B, 31, 1406 (1975). S. Van Smaalen, Crystallogr. Rev.,4, 79 (1995). T. Janssen, A. Janner, Adv. Phy., 36, 519 (1987). S. Schmid, J. G. Thompson, A. D. Rae, B. D. Butler, R. L. Withers, Acta Crystallogr., Sect. B, 51, 698 (1995); A. D. Rae, S. Schmid, J. G. Thompson, R. L. Withers, Acta Crystallogr., Sect. B, 51, 709 (1995). 8. S. Schmid, R. L. Withers, J. G. Thompson, J . Solid State Chem., 99, 226 (1992).
1. 2. 3. 4. 5. 6. 7.
3.1 0.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.1 Binary Oxides with Narrow Chemically Insignificant Composition Range
Compositions with extremely small deviations from stoichiometry can be prepared by heating stoichiometric compounds to high temperatures, by exposure to ionizing
158
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.1 Transition Metal Lower Oxides
radiation, and by diffusion of excess metal into stoichiometric compositions or reduction with reducing agents such as H z . All solid oxides will develop oxygen dissociation pressures at sufficiently elevated temperatures. To produce oxygen-deficient, nonstoichiometric surfaces, y - or X-irradiation yields similar effects. Usually, stoichiometry is reestablished by equilibration upon cooling. In certain cases, the reduced metal atoms at the surface will diffuse to inner interstitial sites yielding stable nonstoichiometric compositions. ZnO and CdO are examples of such systems among the representative elements's2. Similar behavior is known for the alkaline earth oxides MgO, CaO, SrO, and Ba03, which are prepared in both oxygen-deficient and metal-rich forms by heating in metal vapors. The resulting nonstoichiometric materials often exhibit spectacular colors (e.g., bright red or blue in the case of BaO). Other posttransition metal oxides, particularly in the higher oxidation states such as T1203,Bi2O3 and P b 0 2 , will lose O 2 upon heating to produce a continuous series of phases that range in stoichiometry from chemically insignificant deviations to genuinely bivariant systems such as those discussed in 3.10.1.5.24. (L. E. CONROY)
1. 2. 3. 4.
S. E. Harrison, Phys. Rev., 93, 52 (1954). W. J. Moore, J . Electrochem. SOC., 100, 302 (1953). P. V. Kovtunenko, Y. L. Kharif, Russ. Chem. Rec., 48(3), 243 (1979). R. L. Sproull, R. S. Bever, G. Libowitz, Phys. Rec., 92, 77-80 (1953).
3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.1 Transition Metal Lower Oxides: TiO, VO, MnO, FeO, COO, NiO, NbO, and Cu,O
All oxides discussed in this section, except CuzO, possess rock salt-related (NaCl) structures. The rock salt structure consists of two interpenetrating face-centered-cubic (fcc) substructures originating at (0 00) and (1/2 1/2 1/2) for the metal and nonmetal atoms, respectively. The C u 2 0 (cuprite) structure can be considered to be an fcc array of Cu atoms with one-fourth of the tetrahedral interstices filled with oxygen atoms in an ordered way. The tetrahedra of metal-coordinated oxygen share corners, creating two apparently independent networks. The precise composition of each nonstoichiometric phase is determined at equilibrium by the temperature and the ambient oxygen fugacity. All are capable of variable composition to different degrees. In the preparation of these nonstoichiometric materials, the oxygen fugacity is normally controlled at the low values required by the gaseous buffers C 0 / C 0 2 or H2/H20, by solid buffers such as Fe-FeO or Ni-NiO, or by an electrochemical cell derived using the oxygen-zirconia system. Except for NbO,. Figure 1 illustrates the temperature and stability composition range of these oxides'. Table 1 shows the maximum homogeneity range of each. Large single crystals of MnO,, COO,, and FeO, are grown by a modified Bridgman technique using crucibleless skull melting2. Subsolidus annealing under CO/CO2 oxygen control assures composition homogeneity. Other crystal growth techniques include flame fusion, arc imaging, flux growth, induction plasma fusion, epitaxial fusion, hydrothermal growth, chemical vapor deposition, grain growth, and Czochralski pulling. Thermodynamic and structural details have been succinctly d e ~ c r i b e d ~ The -~. structural description may focus either on the occurrence of point defects disordered
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
158
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.1 Transition Metal Lower Oxides
radiation, and by diffusion of excess metal into stoichiometric compositions or reduction with reducing agents such as H z . All solid oxides will develop oxygen dissociation pressures at sufficiently elevated temperatures. To produce oxygen-deficient, nonstoichiometric surfaces, y - or X-irradiation yields similar effects. Usually, stoichiometry is reestablished by equilibration upon cooling. In certain cases, the reduced metal atoms at the surface will diffuse to inner interstitial sites yielding stable nonstoichiometric compositions. ZnO and CdO are examples of such systems among the representative elements's2. Similar behavior is known for the alkaline earth oxides MgO, CaO, SrO, and Ba03, which are prepared in both oxygen-deficient and metal-rich forms by heating in metal vapors. The resulting nonstoichiometric materials often exhibit spectacular colors (e.g., bright red or blue in the case of BaO). Other posttransition metal oxides, particularly in the higher oxidation states such as T1203,Bi2O3 and P b 0 2 , will lose O 2 upon heating to produce a continuous series of phases that range in stoichiometry from chemically insignificant deviations to genuinely bivariant systems such as those discussed in 3.10.1.5.24. (L. E. CONROY)
1. 2. 3. 4.
S. E. Harrison, Phys. Rev., 93, 52 (1954). W. J. Moore, J . Electrochem. SOC., 100, 302 (1953). P. V. Kovtunenko, Y. L. Kharif, Russ. Chem. Rec., 48(3), 243 (1979). R. L. Sproull, R. S. Bever, G. Libowitz, Phys. Rec., 92, 77-80 (1953).
3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.1 Transition Metal Lower Oxides: TiO, VO, MnO, FeO, COO, NiO, NbO, and Cu,O
All oxides discussed in this section, except CuzO, possess rock salt-related (NaCl) structures. The rock salt structure consists of two interpenetrating face-centered-cubic (fcc) substructures originating at (0 00) and (1/2 1/2 1/2) for the metal and nonmetal atoms, respectively. The C u 2 0 (cuprite) structure can be considered to be an fcc array of Cu atoms with one-fourth of the tetrahedral interstices filled with oxygen atoms in an ordered way. The tetrahedra of metal-coordinated oxygen share corners, creating two apparently independent networks. The precise composition of each nonstoichiometric phase is determined at equilibrium by the temperature and the ambient oxygen fugacity. All are capable of variable composition to different degrees. In the preparation of these nonstoichiometric materials, the oxygen fugacity is normally controlled at the low values required by the gaseous buffers C 0 / C 0 2 or H2/H20, by solid buffers such as Fe-FeO or Ni-NiO, or by an electrochemical cell derived using the oxygen-zirconia system. Except for NbO,. Figure 1 illustrates the temperature and stability composition range of these oxides'. Table 1 shows the maximum homogeneity range of each. Large single crystals of MnO,, COO,, and FeO, are grown by a modified Bridgman technique using crucibleless skull melting2. Subsolidus annealing under CO/CO2 oxygen control assures composition homogeneity. Other crystal growth techniques include flame fusion, arc imaging, flux growth, induction plasma fusion, epitaxial fusion, hydrothermal growth, chemical vapor deposition, grain growth, and Czochralski pulling. Thermodynamic and structural details have been succinctly d e ~ c r i b e d ~ The -~. structural description may focus either on the occurrence of point defects disordered
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.1 Transition Metal Lower Oxides
159
SINGLE-PHASE REGION
--Ti0 Il
40
Figure 1. Composition variation with oxygen pressure of the monoxides of 3d elements and of C u 2 0 . (Modified from Ref. 1.)
TABLE1. HOMOGENEITY RAKGEAKD EQUILIBRIUM OXYGEN PRESSURES OF 3d OXIDES, MO, Stability Range Oxide
Xmin
X,,,
TiO,
0.65 0.80 1.oo 1.045 1.000 1.000 0.982 0.500
1.25 1.30 1.18 1.200 1.012 1.001 1.008 0.5016
VOX
MnO, FeO, coo,
NiO, NbO, CU20,
Source: Modified from Ref. 1
Oxygen Pressure Range Ax
Maximum
Minimum
APO
0.60 0.50 0.18 0.155 0.012 0.001
44.1 34.5 34.7 20.5 14.5 16.5
41.5 33.2 10.7 19.2 2.5
2.6 1.3 24 1.3 12.0
0.0016
9.6
7.0
2.6
160 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper
3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides
or aggregated on certain crystallographic planes or on the local cluster structure of a localized defect. The structure of the nonstoichiometric phase will depend on the defect concentration, the temperature, and more specifically the nature of the metal atoms. The T i 0 system illustrates the complexity these nonstoichiometric phases. From about 1200-2000K, T i 0 has 15% each of Ti and 0 vacant sites. Below 1200K the vacancies are ordered in a monoclinic structure, B2/m, with Ti and 0 vacancies in every third (lOO),,bic plane. Diffuse X-ray scattering from single crystals at 1323 K shows local order resembling that of the low temperature phase6. Prolonged annealing of Ti01,25at 1070 K produces a tetragonal ordered phase.' An orthorhombic ordered phase in the range Ti00.7-0.9occurs in samples cooled rapidly from the melt and annealed briefly at low temperatures. The vacant Ti and 0 sites in TiOl-d (ca. 15% when 6 = 0 under preparative conditions) can be reduced by applying high pressures at suitable temperatures. At PAT = 90,000 kbar, K they are completely eliminated, with a concomitant increase in lattice parameter and density'. Chemically similar NbO,, which also has a rock salt-like structure, has 25% both Nb and 0 sites vacant but a very small composition range (see Table 1). Here, the vacancies are ordered with the corner atom of each of the interpenatrating fcc lattices missing. This leaves a three-dimensional network of corner-sharing octahedral clusters of Nb atoms, which account for its metallic conductivity. These vacancies are not annihilated at higher oxygen pressures as they are in TiO, and VO,'. (L. EYRING) 1. T. B. Reed, in The Chemistry of Exended Defects in Nonmetallic Solids, L. Eyring, M. O'Keeffe, eds., North-Holland, Amsterdam, 1970, p. 21. 2. H. R. Harrison, R. Aragon, C. J. Sandbert, Muter. Res. Bull., 15, 571 (1980). 3. 0. T. Sorensen, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 1. 4. C. R. A. Catlow, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 61. 5. A. K. Cheetham, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 399. 6. H. Terauchi, J. B. Cohen, Acta Crystallogr., Sect. A , 35, 646 (1979). 7 . D. Watanabe, 0. Teraski, A. Jostsons, J. R. Castles, J . Phys. Soc. Jpn., 25, 292 (1968). 8. A. Taylor, N. J. Doyle, in The Chemistry ofExtended Defects in Non-Metallic Solids. L. Eyring, M. OKeeffe, eds., North-Holland, Amsterdam, 1970, p. 523. 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides (Ce, Pr, and Tb higher oxides)
Of the 14 lanthanide element binary oxide systems, only three (Ce, Pr, and Tb) display prominent tetravalent states attributable to Hund's rule. The phase diagrams of these three oxide systems (Fig. 1) are similar when their temperature and oxygen pressure ranges of study are taken into consideration'. The equilibrium O2 pressure is not explicit in these phase diagrams. The relative stability of an intermediate phase, e.g., R01.818,is revealed by its equilibrium decomposition temperatures and O2 pressures, which are approximately 909 K and Pa, 733 K and 2 x lo4 Pa, and 670 K and 9 x lo3 Pa for Ce, Pr, and Tb oxides, respectively. Each system at its composition limits exhibits trivalent and tetravalent oxides.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
160 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper
3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides
or aggregated on certain crystallographic planes or on the local cluster structure of a localized defect. The structure of the nonstoichiometric phase will depend on the defect concentration, the temperature, and more specifically the nature of the metal atoms. The T i 0 system illustrates the complexity these nonstoichiometric phases. From about 1200-2000K, T i 0 has 15% each of Ti and 0 vacant sites. Below 1200K the vacancies are ordered in a monoclinic structure, B2/m, with Ti and 0 vacancies in every third (lOO),,bic plane. Diffuse X-ray scattering from single crystals at 1323 K shows local order resembling that of the low temperature phase6. Prolonged annealing of Ti01,25at 1070 K produces a tetragonal ordered phase.' An orthorhombic ordered phase in the range Ti00.7-0.9occurs in samples cooled rapidly from the melt and annealed briefly at low temperatures. The vacant Ti and 0 sites in TiOl-d (ca. 15% when 6 = 0 under preparative conditions) can be reduced by applying high pressures at suitable temperatures. At PAT = 90,000 kbar, K they are completely eliminated, with a concomitant increase in lattice parameter and density'. Chemically similar NbO,, which also has a rock salt-like structure, has 25% both Nb and 0 sites vacant but a very small composition range (see Table 1). Here, the vacancies are ordered with the corner atom of each of the interpenatrating fcc lattices missing. This leaves a three-dimensional network of corner-sharing octahedral clusters of Nb atoms, which account for its metallic conductivity. These vacancies are not annihilated at higher oxygen pressures as they are in TiO, and VO,'. (L. EYRING) 1. T. B. Reed, in The Chemistry of Exended Defects in Nonmetallic Solids, L. Eyring, M. O'Keeffe, eds., North-Holland, Amsterdam, 1970, p. 21. 2. H. R. Harrison, R. Aragon, C. J. Sandbert, Muter. Res. Bull., 15, 571 (1980). 3. 0. T. Sorensen, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 1. 4. C. R. A. Catlow, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 61. 5. A. K. Cheetham, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 399. 6. H. Terauchi, J. B. Cohen, Acta Crystallogr., Sect. A , 35, 646 (1979). 7 . D. Watanabe, 0. Teraski, A. Jostsons, J. R. Castles, J . Phys. Soc. Jpn., 25, 292 (1968). 8. A. Taylor, N. J. Doyle, in The Chemistry ofExtended Defects in Non-Metallic Solids. L. Eyring, M. OKeeffe, eds., North-Holland, Amsterdam, 1970, p. 523. 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides (Ce, Pr, and Tb higher oxides)
Of the 14 lanthanide element binary oxide systems, only three (Ce, Pr, and Tb) display prominent tetravalent states attributable to Hund's rule. The phase diagrams of these three oxide systems (Fig. 1) are similar when their temperature and oxygen pressure ranges of study are taken into consideration'. The equilibrium O2 pressure is not explicit in these phase diagrams. The relative stability of an intermediate phase, e.g., R01.818,is revealed by its equilibrium decomposition temperatures and O2 pressures, which are approximately 909 K and Pa, 733 K and 2 x lo4 Pa, and 670 K and 9 x lo3 Pa for Ce, Pr, and Tb oxides, respectively. Each system at its composition limits exhibits trivalent and tetravalent oxides.
161 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides
A
B 1000
2
2 600
E
g400 E r-" 200 1.50 1.60 1.70 1.80 1.90 2.00
1.50
Composition x, in CeOx
1.60 1.70 1.80 1.90
Composition x, in Prox
2.00
C I
1.50
"
1 ' 1 '
1.60
1.70
"
1.80
"
1.90
I
2.00
Composition x, in TbOx Figure 1. Phase diagrams of the higher oxides of Ce, Pr, and Tb: dashed lines represent regions of incomplete investigation. (From Ref. 1.) At higher temperatures in a suitable O 2 atmosphere, the Ce and P r oxides exist as a CJ phase (related to the C-type sesquioxide structure) with a composition range between R 0 1 . 5 0and RO1.,,,. Beyond R 0 1 . 7 2another widely nonstoichiometric region, a fluorite-type a phase, exists up to R 0 2 . Between these nonstoichiometric phases there is a narrow CJ-!x miscibility gap. As suggested by the dashed curve in Figure lc, the terbium oxide system would likely show similar behavior if higher O 2 pressures were used in its study. The disordered, fluorite-related a phases order at lower temperatures and O2 pressures to yield members of a homologous oxides series. Compositionally and structurally, these ordered intermediate phases are anion-deficient and fluorite-related. No analogous, ordering phenomena develop from the C-type-related CJ phase at lower temperatures. The oxides of Ce, Pr, and T b are prepared in oxygen or air from the decomposition product of some suitable precursor compound, usually oxalate or hydroxide, followed by slow cooling. Decomposition in air yields CeO,, Pr24044,or a mixture of T b 7 0 1 2and Tbl 16 (of approximate composition Tb407), respectively. The homologous series
162 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides
members are obtained from these by adjusting their respective oxygen compositions by annealing at suitably controlled temperatures and 0 , pressures’, according to Table 1, followed by cooling under conditions that prevent a compositional change. Single crystals of CeO, are grown’ from fluxes cooled from temperatures in the vicinity of 1600 K. Lower temperature growth ( < 1100 K) of CeO,, Pro,, and TbOz is accomplished by hydrothermal techniques using 0, pressures of the order of 1700 bar. The ordered intermediate oxides, which decompose peritectoidally at higher temperatures to the disordered x phase, belong to a homologous series of generic formula R n 0 2 n - 2 mwhere , n and m are integers determined as discussed below. The intermediate phases are commensurate superstructures of fluorite. Although the strict fcc symmetry of the unit cell is broken, both the metal and nonmetal atoms remain essentially closepacked fcc. Figure 2 shows a selection of diffraction patterns that illustrate this phenomenon,. The nine strong spots in each pattern are fluorite-type reflections. TABLE1. PREPARATIOY OF THE OXIDES O F Ce, Pr, AND Tb’ Oxide
Phase Designation
F 6 6’ M 19 &
i 1
Q
F 71
P
6
E b
1
4
A C 8(3) 6 6’ 1
4
B
Temperature (K)
1173 909 893 853 873 909 943 988
1003 1244 1113 1173 588 723 513 693 733 (Oxidation) 738 (Reduction) 753 833 1123 823 1273 < 1073 1073 523 808 968 923 1273
Gas (e.g., 0,) Pressure (Pa)
1.01 x 105 10-26
Dry H2 Dry H2 Dry H2 10-25 Dry Hz 10-23.5
Dry H2 10-15.8 Dry H2 Dry Hz 1.01 x 105 5 x 105 5 x 103 4.6 x 104 2 x 104
2 x 104 4 x 103 1.3 x 103 1.3 x 103
H2 (flow) 10-4 lo8 lo8 5 x 104 5 x 104 1.7 x 103 H2 10-4
163 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides
Pr7012
Pr24044
Pr901 6
pr40072
Tb11020
b48088
Figure 2. Electron diffraction patterns of homologous series members. The fluorite reflections are the nine strongest spots in each pattern. Weaker spots are from the supercell structure. Note that super and subcell are commensurate in all cases. Efforts to obtain single crystals adequate for structure determination by X-ray diffraction methods were unfruitful. Fortunately, high resolution electron microscopy (HREM) studies make it possible to obtain the unit cells of most of the stable phases. The structures of five homologous series members have been refined by high resolution neutron powder diffraction methods2-’. These successes make it possible to extract the compositional and structural principle underlying these anion-deficient, fluorite-related oxide systems6. Ionic or electrostatic interactions dominate the forces present in these oxides and determine their stable structures. The shielded 4f electrons do not contribute significantly to the structural form of these oxides, in contrast to the d-d electron orbital overlap in transition metal oxides. Experimental studies provide the integral values of n and m in the generic formula, R,02,-2,, of all possible homologous series members of higher rare earth oxides. The value of n is obtained from the multiplicity of the supercell of fluorite type revealed in suitable electron diffraction patterns. The value of m is obtained from the composition RO,, since m = n (1 - 4 2 ) . With this information and using the structural principle that has been developed6, it is possible to determine the true generic formula and the ideal structure of all ordered phases. Since the superstructures are commensurate with the fluorite subcell, it must be possible to model every ideal structure as a network of fluorite-type modules. Just as
164 3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.2 Oxygen-Deficient, Fluorite-Related Structures: Lanthanide Oxides
there is translational symmetry for the superstructure unit cells, there must be translational symmetry for the rational substructure modules that constitute the superstructures. It is convenient to view the fluorite structure as a close-packed cubic array of metal atoms in which every tetrahedral site is filled with an 0 atom. We focus on the tetrahedrally coordinated nonmetal site, which is filled in the fluorite structure and sometimes vacant in the anion-deficient, fluorite-related structures. It is postulated that any one of the eight 0 atoms in the fluorite-type module is as likely to be removed as any other. Since there is a minimum observed separation of vacancies, there can be only four distinct types of modules: (1) one with no vacant 0 sites designated F; (2) one with one vacant 0 site with the apex of the coordination tetrahedron pointing up, designated U' (there are four orientational variations of this type: U1,U2,U3,U4;(3) one with one vacant 0 site with the apex pointing down, designated Dj(there are also four orientational variants of this type: D1, D1,D3,D4;and (4)one with two vacancies that can exist only if they are paired along the body diagonal of the cube, designated W j (there are four orientational variants of this type: W:, W i , W:, W:. Every stable superstructure in these related materials must contain, in a modular unit volume, an integral number (m)of all eight of the possible ways of having an 0 vacancy in the fluorite-type subcell. Every superstructure will have exactly some multiple of the same eight types of 0 vacancy in periodic repetition. This means that there are equal numbers of tetrahedrally coordinated vacancies pointing up or down in such a way that their electric vectors are in opposition (i.e., m[U1U2U3U4D1D2D3D4], or if a W module is present, the corresponding vacant sites it contains must be omitted from the U and D content). The F module must adjust the composition of series members. Table 2 lists the established higher oxides of the lanthanides. By considering the modular constitution from Table 2, and having in hand the requisite electron diffraction
TABLE 2. UNITCELLCONTENT OF ESTABLISHED MEMBERS OF THE R n 0 2 n - Z m SERIES
Phase Designation (Representatives) 1 Y
L
n
m
Modular Content
7 9 11 12 16 19 24 24 29 39 40 48 62 88
1 1 1 1 1 2 2 2 3 4 4 4 6 8
W3U3D F4U4D 3F4U4D 4F4U4D 8F4U4D 3F8U8D 8F8U8D 8F8U8D 5F 12U 12D 7F16U16D 8F16U16D 16F16U16D 14F24U24D 24F32U32D
Formula, Unit Cell Content
O/R 1.714 1.778 1.818 1.833 1.875 1.789 1.833 1.833 1.793 1.795 1.800 1.833 1.806 1.818
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.3 Oxygen-Excess Fluorite Structures, UO,
165
pattern that shows the modular arrangement in the selected orientation, it is possible to model the ideal structures of all the known phases6. (L. EYRING) 1. R. G. Haire, L. Eyring, in Handbook on the Physics and Chemistry of Rare Earths, K. S. Gschneidner, Jr., L. Eyring, eds., North-Holland, Amsterdam, 1994, p. 413. 2. J. Zhang, R. B. Von Dreele, L. Eyring, The Structures of Tb7OI2and TbI1Oz0,J . Solid State Chem., 104, 21 (1993). 3. J. Zhang, R. B. Von Dreele, L. Eyring, Structures in the Oxygen-Deficient Fluorite-Related RnOZn-2Homologous Series: Pr9O1,, J . Solid State Chem., 118, 133 (1995). 4. J. Zhang, R. B. Von Dreele, L. Eyring, Structures in the Oxygen-Deficient Fluorite-Related R n 0 2 n - ZHomologous Series: Pr10018,J . Solid State Chem., 118, 141 (1995). 5. J. Zhang, R. B. Von Dreele, L. Eyring, Structures in the Oxygen-Deficient Fluorite-Related R,Oz,-z Homologous Series: P r 1 2 0 2 2 J, . Solid State Chem., 122, 53 (1995). 6. Z. C. Kang, L. Eyring, Aust. J . Chem., 49, 981 (1997). 3.1 0.2.2.3 Oxygen-Excess Fluorite Structures, UO,,,
Section 3.10.2.2.2 discussed oxygen-dejcient, fluorite-related compounds. Here we describe the preparation and characterization of oxygen-excess, fluorite-related compounds, UO, d . Fluorite-type UO, can be prepared under severely reducing conditions and reduced further only in the presence of U metal beginning at temperatures approaching 1500 IS. However, UO, will absorb oxygen interstitially forming a nonstoichiometric phase nearly to U 0 2 . 2 5without departing from the basic fluorite structure. Oxides in this composition region are obtained from the higher oxides by reduction with CO or H,. For example', at 1573 K an 0, pressure of 5.0 x l o w 8bar will produce U02.026;5.0 x bar gives U02.115,and a pressure of 7.1 x bar yields u 0 2 . 2 2 4 . The first, ordered higher oxide phase of narrow composition range is reached at U 4 0 9 - y (U02,25). Summaries of thermodynamic and structural i n f o r r n a t i ~ n provide ~-~ an assessment and references. It is known that the oxygens do not occupy only fluorite positions but rather some are shifted along [llo], causing two adjacent U atoms to increase their oxidation state and two 0 atoms on tetrahedral sites to move along [lll], leaving two normal 0 sites vacant. This is the 2 : 2: 2 Willis cluster5. U 4 0 9 - ywas believed to consist of an ordered array of the clusters found in U 0 2 + a . In 1986 the structure of D-U4O9-) was determined6 from single-crystal neutron diffraction data. Excess 0 atoms are included in 13-member clusters centered on the 12-fold positions of the space group I-43d. Clusters result from the corner-sharing of octahedral groupings of U 0 8 square anti prisms, which enclose a cuboctahedron of anions with an additional oxygen atom at the center. The unit cell is U256OS72,which is U 4 0 9 - ywith y = 0.062. Two compositions within the nonstoichiometric region, U 0 2 . 1 and U 0 2 . 1 3 ,have recently been studied7 by neutron diffraction to determine the nature of the defects in UOzta. It had been supposed that U 4 0 9 would be an ordered structure that incorporated the ordered defect structures of the neighboring nonstoichiometric phase. However, these specimens contained two types of 0 interstitial (one type displaced along (1 10) and the other along (1 11)). In the first crystal, the occupation numbers of the three kinds of 0 defect are close to those expected from the formation of 2 : 2 : 2 clusters, whereas in the second crystal the occupation numbers corresponded to those calculated for cuboctahedral clusters that are the ordered features of U 4 0 9- y . It is concluded that the defect structure varies from one sample to another, depending on composition, oxidation
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.2 Binary Oxides with a Wide Composition Range 3.10.2.2.3 Oxygen-Excess Fluorite Structures, UO,
165
pattern that shows the modular arrangement in the selected orientation, it is possible to model the ideal structures of all the known phases6. (L. EYRING) 1. R. G. Haire, L. Eyring, in Handbook on the Physics and Chemistry of Rare Earths, K. S. Gschneidner, Jr., L. Eyring, eds., North-Holland, Amsterdam, 1994, p. 413. 2. J. Zhang, R. B. Von Dreele, L. Eyring, The Structures of Tb7OI2and TbI1Oz0,J . Solid State Chem., 104, 21 (1993). 3. J. Zhang, R. B. Von Dreele, L. Eyring, Structures in the Oxygen-Deficient Fluorite-Related RnOZn-2Homologous Series: Pr9O1,, J . Solid State Chem., 118, 133 (1995). 4. J. Zhang, R. B. Von Dreele, L. Eyring, Structures in the Oxygen-Deficient Fluorite-Related R n 0 2 n - ZHomologous Series: Pr10018,J . Solid State Chem., 118, 141 (1995). 5. J. Zhang, R. B. Von Dreele, L. Eyring, Structures in the Oxygen-Deficient Fluorite-Related R,Oz,-z Homologous Series: P r 1 2 0 2 2 J, . Solid State Chem., 122, 53 (1995). 6. Z. C. Kang, L. Eyring, Aust. J . Chem., 49, 981 (1997). 3.1 0.2.2.3 Oxygen-Excess Fluorite Structures, UO,,,
Section 3.10.2.2.2 discussed oxygen-dejcient, fluorite-related compounds. Here we describe the preparation and characterization of oxygen-excess, fluorite-related compounds, UO, d . Fluorite-type UO, can be prepared under severely reducing conditions and reduced further only in the presence of U metal beginning at temperatures approaching 1500 IS. However, UO, will absorb oxygen interstitially forming a nonstoichiometric phase nearly to U 0 2 . 2 5without departing from the basic fluorite structure. Oxides in this composition region are obtained from the higher oxides by reduction with CO or H,. For example', at 1573 K an 0, pressure of 5.0 x l o w 8bar will produce U02.026;5.0 x bar gives U02.115,and a pressure of 7.1 x bar yields u 0 2 . 2 2 4 . The first, ordered higher oxide phase of narrow composition range is reached at U 4 0 9 - y (U02,25). Summaries of thermodynamic and structural i n f o r r n a t i ~ n provide ~-~ an assessment and references. It is known that the oxygens do not occupy only fluorite positions but rather some are shifted along [llo], causing two adjacent U atoms to increase their oxidation state and two 0 atoms on tetrahedral sites to move along [lll], leaving two normal 0 sites vacant. This is the 2 : 2: 2 Willis cluster5. U 4 0 9 - ywas believed to consist of an ordered array of the clusters found in U 0 2 + a . In 1986 the structure of D-U4O9-) was determined6 from single-crystal neutron diffraction data. Excess 0 atoms are included in 13-member clusters centered on the 12-fold positions of the space group I-43d. Clusters result from the corner-sharing of octahedral groupings of U 0 8 square anti prisms, which enclose a cuboctahedron of anions with an additional oxygen atom at the center. The unit cell is U256OS72,which is U 4 0 9 - ywith y = 0.062. Two compositions within the nonstoichiometric region, U 0 2 . 1 and U 0 2 . 1 3 ,have recently been studied7 by neutron diffraction to determine the nature of the defects in UOzta. It had been supposed that U 4 0 9 would be an ordered structure that incorporated the ordered defect structures of the neighboring nonstoichiometric phase. However, these specimens contained two types of 0 interstitial (one type displaced along (1 10) and the other along (1 11)). In the first crystal, the occupation numbers of the three kinds of 0 defect are close to those expected from the formation of 2 : 2 : 2 clusters, whereas in the second crystal the occupation numbers corresponded to those calculated for cuboctahedral clusters that are the ordered features of U 4 0 9- y . It is concluded that the defect structure varies from one sample to another, depending on composition, oxidation
166
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.1 Doped Oxide Phases
treatment, etc. To know fully the nature and distribution of the defect entities, these studies must be extended to more specimens over the full composition range of the nonstoichiometric phase. (L. EYRING) 1. K. Hagemark, M. Broli, J . Inorg, Nucl. Chem., 28, 2887 (1966). 2. 0. T. Sorensen, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 1. 3. C. R. A. Catlow, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 61. 4. A. K. Cheetham, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 399. 5. B. T. M. Willis, Acta Crystallogr., Sect. A, 34, 88 (1978). 6. D. J. M. Bevan, I. E. Grey, B. M. T. Willis, J . Solid State Chem., 61, 1 (1986). 7. A. D. Murray, B. T. M. Willis, J . Solid State Chem., 84, 52 (1990).
3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.1 Doped Oxide Phases
Distinction between doped phases and substantial substitution (3.10.2.3.5) is made by the criterion that doping is a < 1 % addition. The considerations described below (3.10.2.3.5) regarding homogeneity are equally important for dopants and more difficult to determine because of the low concentrations. Frequently, dopants will congregate at surfaces, dislocations, and other areas where the periodic lattice requirements may be somewhat relaxed. Typically, doping studies are based on measurements of some physical property such as electrical conductivity, Seebeck coefficient, or dielectric or magnetic losses, (3.10.1.1.3).Variations in these properties induced by small additions make them technologically interesting. Doped BaTi03 has been extensively studied and is typical of the problems involved. La-doped BaTi03 covers a wide range of conductivity, shows both positive and negative temperature coefficients of electrical resistivity, and exhibits a marked variation in equilibration or reactivity rate. Substitution of La3+ for Ba2+ occurs because of the similar ionic size. The nature of charge compensation, however, is strongly dependent on the O2 partial pressure (Po*) and temperature. Gravimetric studies' show how the charge-compensating defects change from cation vacancies to Ti3+. Figure 1 plots the defect concentration at 1200°C for La = 0.01 as a function of Po>. At still lower values of Po2, anion vacancies are significant. Besides substitution of large trivalent ions for Ba2+, it is possible to achieve similar effects and charge compensation by substituting smaller, highly charged ions such as Nb5 for the Ti4+. This changing nature of the defects with Po, affects not only physical properties, but also diffusion rates. At low Po,, where the concentration of 0 vacancies is relatively high, the equilibration rate with the atmosphere is rapid; however, at normal O2 partial ~ , ~ pressures, where the cation vacancies dominate, the equilibration rate is S ~ O W and porosity and grain boundaries are more important3.Equilibration rates are important in establishing the final, metastable defect situation, which is ultimately established in these semiconducting titanates or ferrites (3.10.2.3.3 and 3.10.2.3.5)at RT. Cation vacancies are best quenched during the cooling cycle, while the anion vacancies are mobile at lower +
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
166
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.1 Doped Oxide Phases
treatment, etc. To know fully the nature and distribution of the defect entities, these studies must be extended to more specimens over the full composition range of the nonstoichiometric phase. (L. EYRING) 1. K. Hagemark, M. Broli, J . Inorg, Nucl. Chem., 28, 2887 (1966). 2. 0. T. Sorensen, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 1. 3. C. R. A. Catlow, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 61. 4. A. K. Cheetham, in Nonstoichiometric Oxides. 0. T. Sorensen, ed., Academic Press, New York, 1981, p. 399. 5. B. T. M. Willis, Acta Crystallogr., Sect. A, 34, 88 (1978). 6. D. J. M. Bevan, I. E. Grey, B. M. T. Willis, J . Solid State Chem., 61, 1 (1986). 7. A. D. Murray, B. T. M. Willis, J . Solid State Chem., 84, 52 (1990).
3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.1 Doped Oxide Phases
Distinction between doped phases and substantial substitution (3.10.2.3.5) is made by the criterion that doping is a < 1 % addition. The considerations described below (3.10.2.3.5) regarding homogeneity are equally important for dopants and more difficult to determine because of the low concentrations. Frequently, dopants will congregate at surfaces, dislocations, and other areas where the periodic lattice requirements may be somewhat relaxed. Typically, doping studies are based on measurements of some physical property such as electrical conductivity, Seebeck coefficient, or dielectric or magnetic losses, (3.10.1.1.3).Variations in these properties induced by small additions make them technologically interesting. Doped BaTi03 has been extensively studied and is typical of the problems involved. La-doped BaTi03 covers a wide range of conductivity, shows both positive and negative temperature coefficients of electrical resistivity, and exhibits a marked variation in equilibration or reactivity rate. Substitution of La3+ for Ba2+ occurs because of the similar ionic size. The nature of charge compensation, however, is strongly dependent on the O2 partial pressure (Po*) and temperature. Gravimetric studies' show how the charge-compensating defects change from cation vacancies to Ti3+. Figure 1 plots the defect concentration at 1200°C for La = 0.01 as a function of Po>. At still lower values of Po2, anion vacancies are significant. Besides substitution of large trivalent ions for Ba2+, it is possible to achieve similar effects and charge compensation by substituting smaller, highly charged ions such as Nb5 for the Ti4+. This changing nature of the defects with Po, affects not only physical properties, but also diffusion rates. At low Po,, where the concentration of 0 vacancies is relatively high, the equilibration rate with the atmosphere is rapid; however, at normal O2 partial ~ , ~ pressures, where the cation vacancies dominate, the equilibration rate is S ~ O W and porosity and grain boundaries are more important3.Equilibration rates are important in establishing the final, metastable defect situation, which is ultimately established in these semiconducting titanates or ferrites (3.10.2.3.3 and 3.10.2.3.5)at RT. Cation vacancies are best quenched during the cooling cycle, while the anion vacancies are mobile at lower +
3.10.2 Stable Bivariant Oxide Phases: NonstoichiometricOxides Proper 167 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.2 Point Defect Nonstoichiometry in Spinels and Related Oxides
v)
I-
V
-I
w LL w Q
8c %-J
-2
8
-3
k
-4
z 0 z
t
w V
z
0
0
-5
0
'?
-12
-10 -8
-4
-6
-2
-0
LOGlO Po2 Figure 1. Concentration of lattice defects in BaTiO, doped with 1% La at 1200°C
temperatures. Eventually, these atomic defects become set and the electronic defects at RT must accommodate to the resulting situation3.
(P.K. GALLAGHER, E. M. GUNDLACH) 1. D. Hennings, Philips Res. Rep., 31, 516 (1976). 2. N. H. Chan, D. M. Smyth, J . Electrochem. SOC.,123, 1584 (1976). 3. R. Wernicke, Philips Res. Rep., 31, 526 (1976).
3.10.2.3.2 Point Defect Nonstoichiometry in Spinels and Related Oxides
There is high stability in spinels, imparted by their favorable geometric configuration, which has led to a wide composition ranges. The structure is derived from a closepacked cubic array of oxygen ions in which one-eighth of the tetrahedral sites, A, and one-half of the octahedral sites, B, are occupied by cations. The idealized formula is, A B 2 0 4 . This represents the normal spinel in which the octahedral sites are filled with the same element (e.g., MgAl,O,). In the inverse spinel structure, the octahedral B site is occupied by more than one cation type. An example of an inverse spinel is Fe(NiFe)04. A wide range of cations can be accommodated in the spinel structure, but the total charge must be 8 + for the stoichiometric compound.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.2 Stable Bivariant Oxide Phases: NonstoichiometricOxides Proper 167 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.2 Point Defect Nonstoichiometry in Spinels and Related Oxides
v)
I-
V
-I
w LL w Q
8c %-J
-2
8
-3
k
-4
z 0 z
t
w V
z
0
0
-5
0
'?
-12
-10 -8
-4
-6
-2
-0
LOGlO Po2 Figure 1. Concentration of lattice defects in BaTiO, doped with 1% La at 1200°C
temperatures. Eventually, these atomic defects become set and the electronic defects at RT must accommodate to the resulting situation3.
(P.K. GALLAGHER, E. M. GUNDLACH) 1. D. Hennings, Philips Res. Rep., 31, 516 (1976). 2. N. H. Chan, D. M. Smyth, J . Electrochem. SOC.,123, 1584 (1976). 3. R. Wernicke, Philips Res. Rep., 31, 526 (1976).
3.10.2.3.2 Point Defect Nonstoichiometry in Spinels and Related Oxides
There is high stability in spinels, imparted by their favorable geometric configuration, which has led to a wide composition ranges. The structure is derived from a closepacked cubic array of oxygen ions in which one-eighth of the tetrahedral sites, A, and one-half of the octahedral sites, B, are occupied by cations. The idealized formula is, A B 2 0 4 . This represents the normal spinel in which the octahedral sites are filled with the same element (e.g., MgAl,O,). In the inverse spinel structure, the octahedral B site is occupied by more than one cation type. An example of an inverse spinel is Fe(NiFe)04. A wide range of cations can be accommodated in the spinel structure, but the total charge must be 8 + for the stoichiometric compound.
168
3.10.2 Stable Bivariant Oxide Phases: NonstoichiometricOxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.2 Point Defect Nonstoichiometry in Spinels and Related Oxides
Few spinels are completely normal or inverse, and distribution between the two is temperature-dependent, becoming more random with increasing temperature. There is crystallographic nonstoichiometry set up by these site preferences that is not reflected as chemical nonstoichiometry. Some factors that strongly influence site selection are ionic radii, ionic charge, bonding preference (e.g., d 2 s p 3 , sp3, Jahn-Teller effects, etc.) and magnetic exchanges. Chemical nonstoichiometry is generally confined to cation vacancies on the B sites. Charge compensation is accomplished via oxidation of appropriate numbers of the remaining cations. Generally, the equilibrium tolerance of the structure allows for only a few percent of cation vacancies before the precipitation of a second phase' - 3 . Kinetic factors are important, and they allow for a large metastability range in the defect structures when coming from the single-phase Metastability is of extreme technological importance because sintered materials can be prepared at high temperatures, where the desired single-phase stoichiometry and valence state can be achieved. These materails can be utilized in devices at RT, where they are highly metastable. Figure 1 shows extension of the metastable compositions as dashed lines through the phase boundary for the system Mno,,,Zno,33Fez.0804+,.Equilibrium isocompositional lines (solid) are seen to change slopes when traversing the phase boundary.
TE
Figure 1. Diagram of Po, versus 1/T for the composition 53% Fe2O3-30% Mn0-17% ZnO.
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.2 Point Defect Nonstoichiometry in Spinels and Related Oxides
169
2000
1000 25
50
75
MOLE % A1203
Figure 2. Equilibrium phase diagram of Mg0-A1203 in air. (The spinel region is hashed.)
Studies in ferrite systems show virtually immediate precipitation of an FeO p h a ~ e ~The . ~ . phase diagram for the mineral spinel MgAlz04 (Fig. 2) shows that solubility extends toward the higher valent ion with the concomitant cation vacancies. Typical, pronounced temperature dependence of the nonstoichiometry is evident. Metastability can be readily quenched in, and subsequently removed by, moderate thermal annealing. Even at the relatively high temperatures in Fig. 2, complete extension of nonstoichiometry to y-Alz03 cannot be achieved. The analogous, grossly defective spinel y-Fe203 is easily prepared, however, at relatively low temperatures by careful oxidation of Fe304 or dehydration of FeOOH. The ?-Fez03 inverse spinel structure is identical to that of Fe304 except that it contains cation vacancies on octahedral sites. Cation vacancies in The formula of y-Fe203can be thought of as Fe3+(Fe;;3 01,3)04. y-Fez03 show degrees of order/disorder depending on the preparation route6. Other grossly nonstoichiometric spinels are prepared by clever substitution, as discussed later (3.10.2.3.5). The metastable spinel LiMnZO4- x is an interesting battery material because the M n z 0 4skeleton remains intact with insertion and extraction of Li'. Charge compensation is attained by variation of the ratio of Mn3+ to Mn4+. Typically, the model for nonstoichiometry is an oxygen-deficient however, density measurementsg indicate that a metal-excess model may be more appropriate. Syntheses of the basic powders involve conventional, repeated mixing and firing of oxides, carbonates or hydroxides. Coprecipitation, freeze-drying, spray-drying, and
170
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.3 Wide-Range Nonstoichiometry: Perovskite-Derived Structures
sol-gel technique have been used extensively to take advantage of the homogeneity of starting solutions (see 17.2.2).Further information is given in several key reviews"- 1 2 . (P. K. GALLAGHER, E. M. GUNDLACH)
1. 2. 3. 4. 5. 6.
7. 8. 9. 10. 11. 12.
G. D. Rieck, F. C. M. Diessens, Acta Crystallogr., 20, 521 (1966). P. Bracconi, P. K. Gallagher, J . Am. Ceram. Soc., 62, 172 (1979). V. V. Prisedskii, Y. S. Prilipko, Russ. J . Inorg. Cheni., 32, 1619 (1987). E. J. Verwey, P. W. Hayman, Physica, 8, 979 (1949). H. M. O'Bryan, F. R. Monforte, R. Blair, J . Am. Ceram. Soc., 48, 577 (1965). M. P. Morales, C. Pechharroman, T. Gonzalez Carrefio, C. J. Serna, J . Solid State Chem., 108, 158 (1994). A. Yamada, K. Miura, K. Hinokuma, M. Tanaka, J . Electrochem. Soc., 142, 2149 (1995). J. Sugiyama, T. Atsumi, T. Hioki, S. Noda, N. Kamegashira, J . Alloys Comp., 235, 163 (1996). M. Hosoya, H. Ikuta, T. Uchida, M. Wakihara, J . Electrochem. Soc., 144, L52 (1997). C. R. A. Catlow, W. C. Mackrodt, eds., Nonstoichiometric Compounds, Vol. 23 in Adcances in Ceramics, American Ceramic Society, Westerville, OH, 1987. K. Kosuge, Chemistry of Nonstoichiometric Compounds, Oxford University Press, New York, 1994. R. J. D. Tilley, Defect Crystal Chemistry and I t s Applications, Chapman & Hall, New York, 1987.
3.10.2.3.3 Wide-Range Nonstoichiometry: Perovskite-Derived Structures
Perovskites offer a particularly wide nonstoichiometry range. In these minerals, unlike the spinels (3.10.2.3.2), nonstoichiometry extends not only to limited cation vacancies, but also toward extensive anion vacancies. The general formulae are Al -xB03 or A B 0 3 - x . As with spinels, the ideal perovskite structure is based on a close-packed cubic array of oxygen ions except that, in this case, one-fourth of the oxygen ions are replaced by relatively large (A) cations. The smaller cations occupy the octahedral sites (B). The A sites are now 12-fold coordinated in the perovskite instead of tetrahedrally coordinated as in the spinel. Because of this high coordination number, it is in these locations that cation vacancies generally form. This idealized perovskite is cubic; however, most compounds in this general class are variously distorted. Distortions give rise to interesting dielectric, catalytic, semiconducting, and magnetic properties, which make these compounds technologically important. The crystallographic distortions are primarily based on the charges and radii and polarizabilities of the particular A and B cations involved, as well as on the type and concentration of vacancies. The sum of the cation charge must equal 6 + for the stoichiometric compound, but this allows considerable flexibility: (1 + , 5 + ), (2 + , 4 + ), or (3 , 3 ). These structural considerations are described for stoichiometric materials.' These materials are similar to the spinels (3.10.2.3.2)with respect to preparation. However, there are some unique synthetic aspects based on achieving the frequently critical 1 : 1 ratio of A to B ions precisely. The method involves precipitation of unique precursor compounds followed by subsequent calcination in air or 0 2 This . approach closely achieves the desired 1 : 1 ratio, because the excess of either component remains in solution. In addition, the precipitation technique generally permits synthesis at lower temperatures, increasing the accessible ranges of particle size, crystallinity, and oxygen stoichiometry. Examples of such precursors are BaTiO(C20,). 4H2O2and LaCo(CN)6. 5H203.Doping or other minor adjustments to the cation composition can be made at the time of original precipitation, or by subsequent precipitation in slurries of the oxide.
+
+
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
170
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.3 Wide-Range Nonstoichiometry: Perovskite-Derived Structures
sol-gel technique have been used extensively to take advantage of the homogeneity of starting solutions (see 17.2.2).Further information is given in several key reviews"- 1 2 . (P. K. GALLAGHER, E. M. GUNDLACH)
1. 2. 3. 4. 5. 6.
7. 8. 9. 10. 11. 12.
G. D. Rieck, F. C. M. Diessens, Acta Crystallogr., 20, 521 (1966). P. Bracconi, P. K. Gallagher, J . Am. Ceram. Soc., 62, 172 (1979). V. V. Prisedskii, Y. S. Prilipko, Russ. J . Inorg. Cheni., 32, 1619 (1987). E. J. Verwey, P. W. Hayman, Physica, 8, 979 (1949). H. M. O'Bryan, F. R. Monforte, R. Blair, J . Am. Ceram. Soc., 48, 577 (1965). M. P. Morales, C. Pechharroman, T. Gonzalez Carrefio, C. J. Serna, J . Solid State Chem., 108, 158 (1994). A. Yamada, K. Miura, K. Hinokuma, M. Tanaka, J . Electrochem. Soc., 142, 2149 (1995). J. Sugiyama, T. Atsumi, T. Hioki, S. Noda, N. Kamegashira, J . Alloys Comp., 235, 163 (1996). M. Hosoya, H. Ikuta, T. Uchida, M. Wakihara, J . Electrochem. Soc., 144, L52 (1997). C. R. A. Catlow, W. C. Mackrodt, eds., Nonstoichiometric Compounds, Vol. 23 in Adcances in Ceramics, American Ceramic Society, Westerville, OH, 1987. K. Kosuge, Chemistry of Nonstoichiometric Compounds, Oxford University Press, New York, 1994. R. J. D. Tilley, Defect Crystal Chemistry and I t s Applications, Chapman & Hall, New York, 1987.
3.10.2.3.3 Wide-Range Nonstoichiometry: Perovskite-Derived Structures
Perovskites offer a particularly wide nonstoichiometry range. In these minerals, unlike the spinels (3.10.2.3.2), nonstoichiometry extends not only to limited cation vacancies, but also toward extensive anion vacancies. The general formulae are Al -xB03 or A B 0 3 - x . As with spinels, the ideal perovskite structure is based on a close-packed cubic array of oxygen ions except that, in this case, one-fourth of the oxygen ions are replaced by relatively large (A) cations. The smaller cations occupy the octahedral sites (B). The A sites are now 12-fold coordinated in the perovskite instead of tetrahedrally coordinated as in the spinel. Because of this high coordination number, it is in these locations that cation vacancies generally form. This idealized perovskite is cubic; however, most compounds in this general class are variously distorted. Distortions give rise to interesting dielectric, catalytic, semiconducting, and magnetic properties, which make these compounds technologically important. The crystallographic distortions are primarily based on the charges and radii and polarizabilities of the particular A and B cations involved, as well as on the type and concentration of vacancies. The sum of the cation charge must equal 6 + for the stoichiometric compound, but this allows considerable flexibility: (1 + , 5 + ), (2 + , 4 + ), or (3 , 3 ). These structural considerations are described for stoichiometric materials.' These materials are similar to the spinels (3.10.2.3.2)with respect to preparation. However, there are some unique synthetic aspects based on achieving the frequently critical 1 : 1 ratio of A to B ions precisely. The method involves precipitation of unique precursor compounds followed by subsequent calcination in air or 0 2 This . approach closely achieves the desired 1 : 1 ratio, because the excess of either component remains in solution. In addition, the precipitation technique generally permits synthesis at lower temperatures, increasing the accessible ranges of particle size, crystallinity, and oxygen stoichiometry. Examples of such precursors are BaTiO(C20,). 4H2O2and LaCo(CN)6. 5H203.Doping or other minor adjustments to the cation composition can be made at the time of original precipitation, or by subsequent precipitation in slurries of the oxide.
+
+
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.3 Wide-Range Nonstoichiometry: Perovskite-Derived Structures
171
Control of the nature and concentration of vacancies is achieved by substitution for A and/or B cations and by manipulation of the Po, and temperature during the final thermal treatment. An example of a cation-deficient perovskite system is Lil-,Nb03-zx, which is stable over a fairly large range of Li,O deficiency. X-ray diffraction evidence4 shows that this LizO deficiency is compensated by the occupation of Li sites by Nb and the creation of Nb vacancies by the following reaction: 6LiNb03
+ 3Lizo + 5Nb','T* + 4V{{ + Nb& + 150;
(a)
B-site cation deficiencies, though much less common than A-site deficiencies, are possible in perovskites. B-site vacancies occur mainly in hexagonal perovskites, but also occur to a much lesser extent in cubic perovskites: e.g., BaTa,-,O,, LaMn03+,, La-doped PbTi03, La-doped BaTi03. The latter three typically contain some combination of A-site and B-site vacancies. Charge compensation for cation deficiencies in the preceding examples took place via the formation of cation vacancies. However, when oxidizable cations are present, compensation can take place via changes in the cation oxidation state. Charge compensation in the system Lal-,Ti03 (0 < x < 0.33)5 is via the formation of Ti4+ with increasing x. Compositions of this compound are prepared by firing mixtures of LazO3, TiO,, and T i 2 0 3in evacuated SiO, containers. The lattice constant for the cubic phase is proportional to the composition through the entire stoichiometry range. Similar behavior is observed for the analogous V compound, but over a reduced range of nonstoichiometry6. Anion-deficient perovskites are much more prevalent than cation-deficient systems, e.g., CaFe03- - x and CaMnO,-,' (0 < x < 0.5). The stoichiometric compounds CaFe0, and CaMn0, adopt the perovskite structure made up of M 0 6 corner-shared octahedra. In CaFeO,-,, two Fe4+ cations are reduced to Fe3+ for every 0 vacancy that is created. This converts an F e 0 6 octahedron to an FeO, tetrahedron. The composition CaFeO,,, then, adopts the perovskite-derived brownmillerite structure consisting of alternating layers of corner-shared F e 0 6 octahedra and corner-shared F e 0 4 tetrahedra. The CaMn03-, system behaves similarly, except that reduction of two Mn4+ cations results in conversion of two M n 0 6 octahedra to two M n 0 5 square pyramids. Therefore, the structure of the fully reduced CaMn02.j consists of layers of corner-shared square pyramids. Various intermediate phases exist between the fully oxidized and fully reduced phases of both these compounds. Key reviews of this area are available*-'0. (P. K. GALLAGHER, E. M. GUNDLACH)
R. S. Roth, J . Res. Natl. Bur. Std., 58, 75 (1957). H. Potdar, S. Deshpande, S. Date, J . Am. Ceram. Soc., 79, 2795 (1996). Y. Sadaoka, E. Traversa, M. Sakamoto, J . Muter. Chem., 6, 1355 (1996). S. C. Abrahams, P. Marsh, Acta Crystallogr., Sect B, 42, 61 (1986). M. Kestigan, R. Ward, J . Am. Chem. Soc., 77, 6199 (1955). B. C. Tofield, W. R. Scott, J . Solid State Chem., 10, 183 (1974). A. Reller, J. M. Thomas, D. A. Jefferson, M. K. Uppal, Proc. R. SOC.London, Ser. A, 394, 223 (1994). 8. D. M. Smyth, in Properties and Applications of Perowkite-Type Oxides, L. G. Tejuca, J. L. G. Fierro, eds., Dekker, New York, 1993, p. 47. 9. P. Hagenmuller, M. Pouchard, J. C. Grenier, J . Muter. Educ., 12, 297 (1990). 10. C. R. A. Catlow, W. C. Mackrodt, eds., Nonstoichiometric Compounds, Vol. 23, Adcances in Ceramics, American Ceramic Society, Westerville, OH, 1987. 1. 2. 3. 4. 5. 6. 7.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
172
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.4 Wide-Range Nonstoichiometry: 0,-Deficient Fluorite Structures
3.10.2.3.4 Wide-Range Nonstoichiometry: Oxygen-Deficient Fluorite Structures112
The best examples of nonstoichiometric fluorite compounds are mixtures of ZrOz and LnzO3, where Ln represents a rare earth. Extensive studies have resulted from the interest in stabilizing Z r 0 2 for use as a refractory and as an oxide ion conductor. The fluorite structure of the MOz phase has the metal ion coordinated by eight oxide ions, forming a body-centered cube. Such cubes then share edges. Substitution of the trivalent Ln ion into the fluorite structure forms a solid solution, Zrz -2xLnzx04-x,which is stable at elevated temperatures over a wide range of x for many Ln elements. The pyrochlore composition, M 4 0 7 , is reached at x = 0.5, and order-disorder transitions are possible. The pyrochlore structure, formed by the removal of one-eighth of the oxide ions, involves distortion of the cubic coordination about the Zr4+ and a doubling of the unit cell dimensions. The effects of temperature on this transition as a function of Ln ions is shown in a portion of the phase diagram for the Zr02-Gdz03 system (Fig. 1). Both the vacancies and the cations are ordered upon undergoing the transition. The pyrochlore compound accommodates a wide range of nonstoichiometry on either side of the ideal composition: (Zrz-2xM2x)M207-x to Zr2(M2-2xZr2x)07+x. Exact values of x and the temperature of the transition depend on the Ln radius. The transition temperature increases with increasing radius of the Ln, so that for the smallest ion, La3+,the compound ZrLa20, is always ordered and for those larger than Dy3+ the compounds are always disordered. Figure 1 shows that the ordering temperature for ZrzGd2O7is 1550°C. Nonstoichiometry limits for the pyrochlore phase are calculated from the ratio of the average radius of the combined cations over that of Zr4+: at a ratio of 1.2, the
'I
ZrOe - G d 2 0 3
25
30 Y 'o
35
MOLE GdZ 0,
40
Figure 1. ZrOz forms nonstoichiometric mixed oxide with fluorite structure with GdzO3. Around composition Z r 2 G d z 0 7 the , lattice can be pyrochlore type because the 0 vacancies are ordered; maximum pyrochlore structure temperautre of stability is 1550°C. (After Ref. 2.)
3.10.2 Stable Bivariant Oxide Phases: NonstoichiometricOxides Proper 173 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.5 Wide-Range Nonstoichiometry: Mixed Cation Oxides
Zro24
I
Zr2 Nd2 0,
2
Z r 2 Gd2 O7
'
I I
I 0.6 0.4
t
1.8
t
Ln3+ rad/Zr4'
I
I
I1
I
rad.
I I
0.2 0.4 0.6
0.2
L"2 03
0.0 (Zr2 Ln2 0,) MOLE
%o
Figure 2. Nonstoichiometry of Zr,Ln,07 (Ln = rare earth) is deduced from variation of the ratio of ionic radii Ln3' :Zr4+, This ratio must be greater than 1.2. (After Ref. 2.)
fluorite-pyrochlore transition occurs and the approximate nonstoichiometry range in the pyrochlore phase can be read from the intersections at that point. Figure 2 illustrates this for Z r 2 N d 2 0 7and Zr2Gd207. There is excellent agreement between observed and calculated values. Values predicted for G d 2 0 3are 28.7 and 37.5, compared to measured values 29.5 and 37.9 mol%. The calculated values for N d 2 0 3are 18 and 48, compared to observed values of 19.1 and 48.1 mol%. (P. K. GALLAGHER, E. M. GUNDLACH)
1. L. Eyring, in Solid State Chemistry of Energy Conaeresion and Storage, J. B. Goodenough, M. S. Whittingham, eds., American Chemical Society, Washington, D.C., 1977, p. 240. 2. L. E. J. Roberts, in Essays in Structural Chemistry, A. J. Downs, ed., Plenum Press, New York, 1971, p. 264.
3.10.2.3.5 Wide-Range Nonstoichiometry:Mixed Cation Oxides; Induced Valence Effects by Substantial Substitution of Cations Having Different Valency
Direct substitution or replacement of cation Ax+ in a structure By+(x # y ) requires charge compensation in some fashion. Two compensation types are possible-the formation of defects (i,e., interstitials or vacancies), which is universally applicable, and changing the valence of the other ions in the structure, which requires that the new valence state be stable enough to achieve substantial substitution. Also, in the second type of compensation, large differences in atomic radii between the original and replacement ions are not generally possible. Some of the variable valence and ionic radii problems can be alleviated by such multiple substitutions as (Ti4', MgZ+) for 2 ~ e ~ ' .
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.2 Stable Bivariant Oxide Phases: NonstoichiometricOxides Proper 173 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.5 Wide-Range Nonstoichiometry: Mixed Cation Oxides
Zro24
I
Zr2 Nd2 0,
2
Z r 2 Gd2 O7
'
I I
0.6 0.4 I
t
1.8
t
Ln3+ rad/Zr4'
I
I
I1
I
rad.
I I
0.2 0.4 0.6
0.2
L"2 03
0.0 (Zr2 Ln2 0,) MOLE
%o
Figure 2. Nonstoichiometry of Zr,Ln,07 (Ln = rare earth) is deduced from variation of the ratio of ionic radii Ln3' :Zr4+, This ratio must be greater than 1.2. (After Ref. 2.)
fluorite-pyrochlore transition occurs and the approximate nonstoichiometry range in the pyrochlore phase can be read from the intersections at that point. Figure 2 illustrates this for Z r 2 N d 2 0 7and Zr2Gd207. There is excellent agreement between observed and calculated values. Values predicted for G d 2 0 3are 28.7 and 37.5, compared to measured values 29.5 and 37.9 mol%. The calculated values for N d 2 0 3are 18 and 48, compared to observed values of 19.1 and 48.1 mol%. (P. K. GALLAGHER, E. M. GUNDLACH)
1. L. Eyring, in Solid State Chemistry of Energy Conaeresion and Storage, J. B. Goodenough, M. S. Whittingham, eds., American Chemical Society, Washington, D.C., 1977, p. 240. 2. L. E. J. Roberts, in Essays in Structural Chemistry, A. J. Downs, ed., Plenum Press, New York, 1971, p. 264.
3.10.2.3.5 Wide-Range Nonstoichiometry:Mixed Cation Oxides; Induced Valence Effects by Substantial Substitution of Cations Having Different Valency
Direct substitution or replacement of cation Ax+ in a structure By+(x # y ) requires charge compensation in some fashion. Two compensation types are possible-the formation of defects (i,e., interstitials or vacancies), which is universally applicable, and changing the valence of the other ions in the structure, which requires that the new valence state be stable enough to achieve substantial substitution. Also, in the second type of compensation, large differences in atomic radii between the original and replacement ions are not generally possible. Some of the variable valence and ionic radii problems can be alleviated by such multiple substitutions as (Ti4', MgZ+) for 2 ~ e ~ ' .
174
3.10.2 Stable Bivariant Oxide Phases: Nonstoichiometric Oxides Proper 3.10.2.3 Multiple Oxides with Point Defect and Defect Complex Equilibria 3.10.2.3.5 Wide-Range Nonstoichiometry: Mixed Cation Oxides
Consideration must be given to whether the substitution has been homogeneous, in either a truly random manner or in a completely ordered but uniformly distributed fashion. Pairing of the substituted ion with its charge-compensating entity does not preclude their homogeneous distribution, but it can markedly influence some physical properties. Conversely, partial segregation can occur in many ways (e.g., by clustering of ions and defects, by concentration at interfaces, or by formation of microdomains prior to nucleation of a new phase). Metastability is also a concern. Equilibrium is facilitated by enhancing diffusion, e.g., by raising the temperature or transient defect concentrations, or by reducing the diffusion path length through better mixing. Charge compensation by large vacancy concentrations is generally a metastable situation at lower temperatures, (e.g. y-Fez03: 3.10.2.3.3) in the case of cation vacancies and Zr2Gd207(see 3.10.2.3.4)for the case of anion vacancies. Ion exchange techniques offer a synthetic route to preparation of many highly deficient substituted spinels'. The method involves replacement of several lower valent ions by exchange with a higher valent ion: 2Lif-+M2
(a)
+
An intimate mixture of an appropriate oxide and excess sulfate reacts during 1-2 weeks at 300-700°C: L i f M 2+ (T: +Li+)O8+ M'2 + SO,-+M 2+M!2+(T:+)O, + Li2S04 (T = Ge, Ti, Mn; M, M'
= Zn,
Co, Mg, Mn, Ni, Cd)
0.04 0.03 u
U
0.02 0.01
01
800
I
900
I
I
I
1000 1100 1200 T EMPER ATUR E ( O C
I
1300
Figure 1. Values for vacancy content (a,) at the spinel-hematite phase boundary: open solid points, Ni or Ni-Zn ferrite'. Plot shows gravimetric points, Mn-Zn data4s5(circles)and represent Fez+ analysis with substitutions (squares). (After Refs. 4, 5.)
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.1 Rutile-Related Structures
175
Cation vacancies on the B sites of the spinel are ordered as in y-Fe203.These highly defective, metastable spinel structures exsolve a higher valent oxide phase MM'(TS)Os-+M(M'T)04
+ 2T02
(c)
at 33O-90O3C, depending on the ions involved. The technique is not limited to spinels'. More conventional substitutions performed at higher temperatures generally achieve charge compensation by combining vacancy formation and valence change, if possible. Analytical studies allow estimations of the relative contributions of the two mechanisms; e.g., the dissolution of T i 0 2 into NiFe204 at 1150°C in 10% 02/90% N 2 involves a charge compensation that occurs 16% by cation vacancy formation and 84% by Fe2' formation2. The proportion occurring via cation vacancy formation decreases with decreasing Po, and increasing temperature as predicted. As the cation vacancy concentration is built up by such substitutions, a threshold is reached at which a second phase precipitates. This phase boundary threshold is independent of whether the vacancies are induced by substitution or by variations in the temperature and Po,. Figure 1 shows how the critical vacancy content varies with temperature for two spinels'. There is a greater tolerance for vacancies in Ni-Zn ferrite than in Mn-Zn ferrite3-'. (P. K. GALLAGHER, E. M. GUNDLACH) 1. J. C . Joubert, G. Berthet, E. F. Bertaut, in Problems of Nonstoichiometry, A. Rabenau, ed., Elsevier, New York, 1970, p. 179. 2. P. K. Gallagher, D. W. Johnson, Jr., H. Schreiber, Jr., E. M. Vogel, J . Solid State Chem., 35, 215 (1980). 3. D. W. Johnson, Jr., M. F. Yan, H. Schreiber, Jr., J . Solid State Chem., 30, 299 (1979). 4. P. I. Slick, in Ferrites: Proceedings of an International Conference, Y. Hashino, S. Iida, M. Sugimoto, eds., University of Tokyo Press, Tokyo, 1971, p. 191. 5. P. Bracconi, P. K. Gallagher, J . Am. Ceram. SOC.,62, 172 (1979).
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures
3.10.3.1.1 Rutile-Related Structures
Some compounds form with the rutile structure or its distorted variants. Only T i 0 2 and V 0 2 and some related ternary oxides have so far been shown to support oxygen loss by the formation of crystallographic shear (CS) planes'-8. Two oxides, s1-10~~ and NbO2" definitely do not form CS planes. The situation in CrOl suggests that CS planes might occur when C r 0 2 is reduced". The oxides Vn02,-1 (4 < n < 8) were the first rutile-type CS reported. At small degrees of reduction V 0 2 coexists with V801s12. The analogous Ti,Oz,-l oxides (4 < n < 10) and the Ti,-2CrZ02n-l oxides (6 < n < 8) exist. Determination of the TiSO9crystal structure allowed clarification of the structural geometry. The CS plane in these compounds is (121) and the CS vector is f(lO1). In the phase range between T i 0 2 and ca. Ti01.93,oxygen loss is taken up on (132) planes. At low degrees of reduction these are at random, but as the degree of reduction increases, ordered arrays form. These produce members of a homologous series of oxides Ti,Oz,-l, with values of n varying from 15 to ca. 40 and a CS vector of f(lO1). In the
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.1 Rutile-Related Structures
175
Cation vacancies on the B sites of the spinel are ordered as in y-Fe203.These highly defective, metastable spinel structures exsolve a higher valent oxide phase MM'(TS)Os-+M(M'T)04
+ 2T02
(c)
at 33O-90O3C, depending on the ions involved. The technique is not limited to spinels'. More conventional substitutions performed at higher temperatures generally achieve charge compensation by combining vacancy formation and valence change, if possible. Analytical studies allow estimations of the relative contributions of the two mechanisms; e.g., the dissolution of T i 0 2 into NiFe204 at 1150°C in 10% 02/90% N 2 involves a charge compensation that occurs 16% by cation vacancy formation and 84% by Fe2' formation2. The proportion occurring via cation vacancy formation decreases with decreasing Po, and increasing temperature as predicted. As the cation vacancy concentration is built up by such substitutions, a threshold is reached at which a second phase precipitates. This phase boundary threshold is independent of whether the vacancies are induced by substitution or by variations in the temperature and Po,. Figure 1 shows how the critical vacancy content varies with temperature for two spinels'. There is a greater tolerance for vacancies in Ni-Zn ferrite than in Mn-Zn ferrite3-'. (P. K. GALLAGHER, E. M. GUNDLACH) 1. J. C . Joubert, G. Berthet, E. F. Bertaut, in Problems of Nonstoichiometry, A. Rabenau, ed., Elsevier, New York, 1970, p. 179. 2. P. K. Gallagher, D. W. Johnson, Jr., H. Schreiber, Jr., E. M. Vogel, J . Solid State Chem., 35, 215 (1980). 3. D. W. Johnson, Jr., M. F. Yan, H. Schreiber, Jr., J . Solid State Chem., 30, 299 (1979). 4. P. I. Slick, in Ferrites: Proceedings of an International Conference, Y. Hashino, S. Iida, M. Sugimoto, eds., University of Tokyo Press, Tokyo, 1971, p. 191. 5. P. Bracconi, P. K. Gallagher, J . Am. Ceram. SOC.,62, 172 (1979).
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures
3.10.3.1.1 Rutile-Related Structures
Some compounds form with the rutile structure or its distorted variants. Only T i 0 2 and V 0 2 and some related ternary oxides have so far been shown to support oxygen loss by the formation of crystallographic shear (CS) planes'-8. Two oxides, s1-10~~ and NbO2" definitely do not form CS planes. The situation in CrOl suggests that CS planes might occur when C r 0 2 is reduced". The oxides Vn02,-1 (4 < n < 8) were the first rutile-type CS reported. At small degrees of reduction V 0 2 coexists with V801s12. The analogous Ti,Oz,-l oxides (4 < n < 10) and the Ti,-2CrZ02n-l oxides (6 < n < 8) exist. Determination of the TiSO9crystal structure allowed clarification of the structural geometry. The CS plane in these compounds is (121) and the CS vector is f(lO1). In the phase range between T i 0 2 and ca. Ti01.93,oxygen loss is taken up on (132) planes. At low degrees of reduction these are at random, but as the degree of reduction increases, ordered arrays form. These produce members of a homologous series of oxides Ti,Oz,-l, with values of n varying from 15 to ca. 40 and a CS vector of f(lO1). In the
176
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.1 Rutile-Related Structures
composition range between approximately Ti01.90and Ti01.93,between the (121) and (132) CS series, the CS planes take intermediate indices. In this region the change in metal-to-oxygen ratio occurs by either a change in the CS plane itself, or in the spacing between the CS planes. Reduction of TiOz appears as the replacement of Ti4+ by Ti3 ions, so reaction with other trivalent oxides of cations similar in size to Ti3+yield phases similar to those in the binary system. Although these are ternary systems, the chemistry is essentially that of the binary oxide and will be included here. The Crz03-Ti02 and binary Ti-0 systems behave similarly. Initial reaction with C r z 0 3leads to (132) CS planes, which yield (121) CS planes at compositions below ca. (Cr, Ti)01,9.Between (Cr, Ti)O1.93 and (Cr, Ti)01.90,a swinging CS plane region exists in which the CS planes may take any indices between (132) and (121). In the VzO3-TizO3-TiO2 system, the (121) phases assume compositions similar to those in the Cr203-Ti02 system (viz., Ti,-zV202n- with solid solution between these materials and the Ti,Oz,The Fe-Ti-0 system shows complex CS behavior at high temperatures. At 1450 K CS occurs over a narrow composition range of ca. (Fe,Ti)01.934[corresponding to n = 16 of the (121) series] to ca. (Fe, Ti)O1.956 [corresponding to n = 75 of the (253) series]. At higher temperatures the CS planes change reversibly from the (121)-( 132) set to (020);at high temperatures, CS phase based on (020) CS planes form. In the intermediate temperature region, wavelike CS occurs. Wavelengths are apparently controlled by elastic strain. When Mn is introduced into the TiOZ-TizO3 system, it is able to substitute into the (121) CS series to approximately 1-2 atom%I5. Microstructures occurring in the slightly reduced rutile region are still unknown. The TiOz-Gaz03 system shows CS behavior at temperature above 1373 K. The CS lies on (210) and appears structurally as an intergrowth of lamellae of the fl-GazO3 structure with the rutile structure along (210) planes. At low G a 2 0 3concentrations, the CS planes are arranged randomly, but increased GazO3 concentration yields the homologous series Ga4Tim-402m-2. At 1623 K, m assumes values between 15 and 31. Much of the information summarized here is treated in more detail in the review articles1-'. +
(R. J. D. TILLEY)
1. L. A. Bursill, B. G. Hyde, Prog. Solid State Chem., 7, 177 (1972). An especially important reference. 2. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 3. I. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids, Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 4. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 5. R. J. D. Tilley, in M T P International Reciews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. I. Roberts, ed., Butterworths, London, 1975, p. 73. 6. B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O'Keeffe, Annu. Rev. Muter. Sci., 4, 43 (1974). 7. R. J. D. Tilley, in Chemical Physics ofSolids and Their Surfaces, Vol. 8, M. W. Roberts, J. M. Thomas, eds., Royal Society of Chemistry, Cambridge 1980, p. 121. 8. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 9. D. Pyke, R. Reid, R. J. D. Tilley, J . Solid State Chem., 25, 1636 (1978). 10. J. R. Gannon, R. J. D. Tilley, J . Solid State Chem., 20, 331 (1977). 11. M. A. Alario Franco, J. M. Thomas, R. D. Shannon, J. Solid State Chem., 9, 261 (1974).
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Bina Oxides: CrystallographicShear Structures 3.10.3.1.2 Re8,-Related Structures; Molybdenum and Tungsten Oxides 12. 13. 14. 15.
177
J. R. Gannon, R. J. D. Tilley, J . Solid State Chem., 25, 301 (1978). B. Brach, I. E. Grey, C. Li, J . Solid State Chem., 20, 29 (1977). K. Kosuge, S. Kachi, Chem. Scripta, 8, 70 (1975). I. E. Grey, C. Li, A. F. Reid, J . Solid State Chem., 17, 343 (1978).
3.10.3.1.2 Re0,-Related Structures: Molybdenum and Tungsten Oxides
The first CS phases reported were the molybdenum oxides MoBOz, and Mo9OZ6 and the tungsten oxide WzOOs8.Since then several phases closely related to these structures have been discovered.'-'. In the binary tungsten-oxygen system, initial reduction leads to formation of isolated (102) CS planes with a CS vector of $(lOl). As reduction increases, these planes order, producing members of the homologous series W n 0 3 n - l ,where n takes integral values down to ca. 16, corresponding to a composition of ca. wo2,93. Below this composition, (103) CS planes with the same CS vector are preferred. At these degrees of reduction, the CS planes are fairly well ordered and the oxides belong to the homologous n taking integral values from ca. 25 to 18. The phase ranges of both series W n 0 3 n - 2with , the (102) and (103) series appears to depend on temperature, with the (103) series existing over a wider composition range at higher temperatures. A region of swinging CS planes between the (102) and (103) series is unknown, but it appears that disordered CS planes containing fragments of (102) and (103) types are common". Small defects in nonstoichiometric W 0 3--x have been interpreted as precursors of CS planes". Oxidation of W03-, CS phases containing ordered (103)CS planes has been studied". Partly oxidized material consisted of mainly large areas of W 0 3 and regions of unchanged CS structure. The solid state chemistry of the CS phases that form when W 0 3 reacts with NbzOs, TazOs, and Ti is analogous to that in the binary system and is mentioned here even though these products are not strictly binary oxides. In the Taz05-W03 system, a series of (103) based CS phases froms at temperatures above about 1200°C with compositions lying between (W, Ta)360106 and (W, Ta)510151.N o extensive (102) series forms, but low densities of isolated (102) CS planes are also found in this system. In the NbZO5-WO3 system, neither (102) nor (103) CS phases form in any amounts, but here the CS planes lie on (104) and (OOl), giving rise to series (Nb,W)n03n-2for ordered (104) CS and (Nb, W)n03n-lfor ordered (001) CS. These occupy the approximate composition range (Nb, W)0z,90-(Nb,W)02.95;the (001) CS series occupies the more reduced part of this range and the (104) series the part near to (Nb, W)O2.95. With the Ti-W-0 system, (001)-derived CS phases are also found, at composition regions assumed Tio.zW03,but they appear to be metastable, and further investigation is desirable. When MOO, is slightly reduced, disordered CS planes form on (120) planes. Upon greater reduction M o 8 0 z 3and Mo9Oz6 are (102) CS phases existing at temperatures above ca. 1000 K. On the composition line between MogOZ6and WO, a homologous series of phases. (Mo, W),03,- exists where n takes values between 10 and ca. 16: in an equilibrium situation, this series contains mainly the even n values. Some range is allowed in the Mo: W ratio, but the meta1:oxygen ratio appears to be invariant for each oxide. In addition to compounds derived from an Re03-type framework, two other CS structures occur in the binary Mo-0 system near to MOO,. These are more stable at lower temperatures than the former group and comprise the ordered series M O , , O ~ ~ - ~ (18 < n < 22). Formation and reduction of many of these CS phases were observed in the electron microscope. For the MOO, - x oxides at low temperatures some ordered oxygen vacancy
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Bina Oxides: CrystallographicShear Structures 3.10.3.1.2 Re8,-Related Structures; Molybdenum and Tungsten Oxides 12. 13. 14. 15.
177
J. R. Gannon, R. J. D. Tilley, J . Solid State Chem., 25, 301 (1978). B. Brach, I. E. Grey, C. Li, J . Solid State Chem., 20, 29 (1977). K. Kosuge, S. Kachi, Chem. Scripta, 8, 70 (1975). I. E. Grey, C. Li, A. F. Reid, J . Solid State Chem., 17, 343 (1978).
3.10.3.1.2 Re0,-Related Structures: Molybdenum and Tungsten Oxides
The first CS phases reported were the molybdenum oxides MoBOz, and Mo9OZ6 and the tungsten oxide WzOOs8.Since then several phases closely related to these structures have been discovered.'-'. In the binary tungsten-oxygen system, initial reduction leads to formation of isolated (102) CS planes with a CS vector of $(lOl). As reduction increases, these planes order, producing members of the homologous series W n 0 3 n - l ,where n takes integral values down to ca. 16, corresponding to a composition of ca. wo2,93. Below this composition, (103) CS planes with the same CS vector are preferred. At these degrees of reduction, the CS planes are fairly well ordered and the oxides belong to the homologous n taking integral values from ca. 25 to 18. The phase ranges of both series W n 0 3 n - 2with , the (102) and (103) series appears to depend on temperature, with the (103) series existing over a wider composition range at higher temperatures. A region of swinging CS planes between the (102) and (103) series is unknown, but it appears that disordered CS planes containing fragments of (102) and (103) types are common". Small defects in nonstoichiometric W 0 3--x have been interpreted as precursors of CS planes". Oxidation of W03-, CS phases containing ordered (103)CS planes has been studied". Partly oxidized material consisted of mainly large areas of W 0 3 and regions of unchanged CS structure. The solid state chemistry of the CS phases that form when W 0 3 reacts with NbzOs, TazOs, and Ti is analogous to that in the binary system and is mentioned here even though these products are not strictly binary oxides. In the Taz05-W03 system, a series of (103) based CS phases froms at temperatures above about 1200°C with compositions lying between (W, Ta)360106 and (W, Ta)510151.N o extensive (102) series forms, but low densities of isolated (102) CS planes are also found in this system. In the NbZO5-WO3 system, neither (102) nor (103) CS phases form in any amounts, but here the CS planes lie on (104) and (OOl), giving rise to series (Nb,W)n03n-2for ordered (104) CS and (Nb, W)n03n-lfor ordered (001) CS. These occupy the approximate composition range (Nb, W)0z,90-(Nb,W)02.95;the (001) CS series occupies the more reduced part of this range and the (104) series the part near to (Nb, W)O2.95. With the Ti-W-0 system, (001)-derived CS phases are also found, at composition regions assumed Tio.zW03,but they appear to be metastable, and further investigation is desirable. When MOO, is slightly reduced, disordered CS planes form on (120) planes. Upon greater reduction M o 8 0 z 3and Mo9Oz6 are (102) CS phases existing at temperatures above ca. 1000 K. On the composition line between MogOZ6and WO, a homologous series of phases. (Mo, W),03,- exists where n takes values between 10 and ca. 16: in an equilibrium situation, this series contains mainly the even n values. Some range is allowed in the Mo: W ratio, but the meta1:oxygen ratio appears to be invariant for each oxide. In addition to compounds derived from an Re03-type framework, two other CS structures occur in the binary Mo-0 system near to MOO,. These are more stable at lower temperatures than the former group and comprise the ordered series M O , , O ~ ~ - ~ (18 < n < 22). Formation and reduction of many of these CS phases were observed in the electron microscope. For the MOO, - x oxides at low temperatures some ordered oxygen vacancy
178
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.3 Niobium Oxides and Related Structures
arrangement gives way to CS planes through aggregation of the vacancies and subsequent collapse of the crystal matrix. In the binary W-0 CS phases, new CS planes grow between neighbors without needing a point defect population in the bulk and at positions in the solid that are governed by the elastic strain field around the CS planes. (R. J. D. TILLEY)
1. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 2. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties ofSolids, Vol. 3. M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 3. R. J. D. Tilley, in M T P International Reciews of Science, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 4. R. J. D. Tilley, in M T P International Reciews of Science, Inorganic Chemistry, Ser, 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 5 . B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O’Keeffe, Annu. Rec. Muter. Sci., 4, 43 (1974). 6. R. J. D. Tilley, in Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M. Thomas, eds., Royal Society of Chemistry, Cambridge, 1980, p. 121. 7. T. Ekstrom, R. J. D. Tilley, Chern. Scripta, 16, 1, (1980). 8. R. J. D. Tilley, Int. J . Refract. Met. Hard Muter., 13, 93 (1995). 9. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 10. W. Sahle, M. Sundberg, Chem. Scripta, 22, 248 (1983). 11. L. A. Bursill, J . Solid State Chem., 48, 256 (1983). 12. W. Sahle, J. Kljavins, J . Solid State Chem., 56, 255 (1985).
3.10.3.1.3 Niobium Oxides and Related Structures
The highest oxide of niobium, Nb205, exists in several structurally closely related polymorphic modifications (Fig. la). If the oxygen-to-metal ratio is changed slightly from 2.5000, either by reduction of Nb205 (using lower oxides and sealed tube techniques or by gas buffer) closely related structures appear. The situation is made more chemically complex when reaction with other materials is considered. Many oxides containing cations similar in size to Nb5+ can react with NbzO5 at elevated temperatures to form phases in which the O/M ratio is somewhat less than 2.500, e.g., TiNb24062 (MO2.4800),or somewhat greater than 2.500, as in WNb12033(M02.5385). In addition, F-ions can partly replace 0’- ions, as in Nb31077F;smaller ions with a preference for tetrahedral sites can also be incorporated into the structure (e.g., PNbl and CeNb1,029). Thus Nb2O5 is able to react with almost all oxides and fluorides of smaller or medium-sized ions, forming many distinct and discrete phases with overall O/M ratios falling between the approximate limits of MO2.4000 to MO2.7000.Although many such compounds have already been described, systematic work will reveal many Although the chemical formulas of these oxides are complex, the structures of most these materials are closely related to the R e 0 3 structure type and can be described in a systematic fashion. The present phases are made up of columns of this structure packed together such that the column axes are aligned and parallel to the crystallographic b axis. The columns are square or rectangular in cross section, with the dimensions m x n octahedra in projection and infinite length. The repeat distance along the b axis is short, frequently corresponding to one octahedron diagonal, while the other axes are much longer. Structural drawings are often shown projected onto (OlO), and in this representation, the columns in cross section resemble blocks packed together. This gives rise to the
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
178
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.3 Niobium Oxides and Related Structures
arrangement gives way to CS planes through aggregation of the vacancies and subsequent collapse of the crystal matrix. In the binary W-0 CS phases, new CS planes grow between neighbors without needing a point defect population in the bulk and at positions in the solid that are governed by the elastic strain field around the CS planes. (R. J. D. TILLEY)
1. J. S. Anderson, in Surface and Defect Properties ofSolids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 2. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties ofSolids, Vol. 3. M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 3. R. J. D. Tilley, in M T P International Reciews of Science, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279. 4. R. J. D. Tilley, in M T P International Reciews of Science, Inorganic Chemistry, Ser, 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 5 . B. G. Hyde, A. N. Bagshaw, S. Anderson, M. O’Keeffe, Annu. Rec. Muter. Sci., 4, 43 (1974). 6. R. J. D. Tilley, in Chemical Physics of Solids and Their Surfaces, Vol. 8, M. W. Roberts, J. M. Thomas, eds., Royal Society of Chemistry, Cambridge, 1980, p. 121. 7. T. Ekstrom, R. J. D. Tilley, Chern. Scripta, 16, 1, (1980). 8. R. J. D. Tilley, Int. J . Refract. Met. Hard Muter., 13, 93 (1995). 9. B. G. Hyde, S. Anderson, Inorganic Crystal Structures, Wiley-Interscience, New York, 1989. 10. W. Sahle, M. Sundberg, Chem. Scripta, 22, 248 (1983). 11. L. A. Bursill, J . Solid State Chem., 48, 256 (1983). 12. W. Sahle, J. Kljavins, J . Solid State Chem., 56, 255 (1985).
3.10.3.1.3 Niobium Oxides and Related Structures
The highest oxide of niobium, Nb205, exists in several structurally closely related polymorphic modifications (Fig. la). If the oxygen-to-metal ratio is changed slightly from 2.5000, either by reduction of Nb205 (using lower oxides and sealed tube techniques or by gas buffer) closely related structures appear. The situation is made more chemically complex when reaction with other materials is considered. Many oxides containing cations similar in size to Nb5+ can react with NbzO5 at elevated temperatures to form phases in which the O/M ratio is somewhat less than 2.500, e.g., TiNb24062 (MO2.4800),or somewhat greater than 2.500, as in WNb12033(M02.5385). In addition, F-ions can partly replace 0’- ions, as in Nb31077F;smaller ions with a preference for tetrahedral sites can also be incorporated into the structure (e.g., PNbl and CeNb1,029). Thus Nb2O5 is able to react with almost all oxides and fluorides of smaller or medium-sized ions, forming many distinct and discrete phases with overall O/M ratios falling between the approximate limits of MO2.4000 to MO2.7000.Although many such compounds have already been described, systematic work will reveal many Although the chemical formulas of these oxides are complex, the structures of most these materials are closely related to the R e 0 3 structure type and can be described in a systematic fashion. The present phases are made up of columns of this structure packed together such that the column axes are aligned and parallel to the crystallographic b axis. The columns are square or rectangular in cross section, with the dimensions m x n octahedra in projection and infinite length. The repeat distance along the b axis is short, frequently corresponding to one octahedron diagonal, while the other axes are much longer. Structural drawings are often shown projected onto (OlO), and in this representation, the columns in cross section resemble blocks packed together. This gives rise to the
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.3 Niobium Oxides and Related Structures
179
(b)
Figure 1. Slightly idealized structures of some niobium oxide block structures: (a) H-Nb205, (b) M-Nb205, (c) W3Nb14044,and (d) Ti2Nb10029(monoclinic form). In each drawing the M 0 6 octahedra are represented by squares, those lighter are displaced by half an octahedron from those darker in outline. The stuctures contain columns of stucture of composition M 0 3 , similar to that of W 0 3 .
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.3 Niobium Oxides and Related Structures
(d)
Figure 1. (Continued).
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.1 Binary Oxides: Crystallographic Shear Structures 3.10.3.1.3 Niobium Oxides and Related Structures
181
common name of “block structures” for these materials. Some representative examples are shown in Fig. la. Neighboring columns are united by edge-sharing of the boundary metal-oxygen octahedra, equivalent to short segments of CS planes parallel to (100) and (001); this amounts to face-sharing of adjacent columns or “blocks”. We can have three different linkages at the corners of the columns: (1) unshared, providing a string of possible cation sites with tetrahedral geometry, found in WNb12033,(2) shared corner octahedron edges at the same level, to link blocks at this corner, found in M-Nb205, or (3) block overlap at the same level, found in Nbl2OZ9. The block structures are able to accommodate small changes in O/M stoichiometry because of the extremely flexible way that blocks can join together. Block sizes can vary; in general larger blocks take the stoichiometry towards M 0 3 while smaller blocks take it toward M 0 2 . Changes in the corner linkages further allow for changes in anion-tocation ratio. If the columns are m x n x x octahedra, the stoichiometry of the block structure containing them is given by:
2
Mmnp+ 103mnp-p(m+n)+4
I
where p is the length of the block ribbons linked at corners by junctions of types (2) and (3) above, and we have to sum over the i block types present. Operationally, many of these phases have apparent stoichiometry ranges that are due to the coherent intergrowth of blocks of the “wrong size” in the matrix of the parent compounds. These may exist as isolated blocks or small groups of blocks, or sheets or larger regions of coherent intergrowth. There is considerable uncertainty over whether these phases can have a composition range due to point defects. Present evidence suggests that this is so, particularly when extra cations are placed in the tetrahedral sites at block corners; but other point defects, including oxygen vacancies, have been reported to occur in these phases6-12. Further work to clarify this aspect of the structural chemistry of these phases is required. However, it has been shown that many “defects” are part of a long-range s t r ~ c t u r e ’ ~ . Despite their structural complexity, the block structures can rearrange structurally very quickly. Splat-cooled material is mostly well ordered14. Complete reaction between H-Nb205 and M o o 3 vapor takes place at about 1273 K. The reduced oxides of Nb, such as Nbl2OZ9,oxidize very rapidly at temperatures as low as 423-673 K. The original structure is mantained in this reaction, and the location of the oxygen in the structure is uncertain. Annealing at higher temperatures produces a remarkable series of solid state transformations in which the original block structure gradually changes to that of H-Nb20515s16.Reaction between H-Nb205 and W 0 3 vapors confirms that these complex structures rearrange with surprising facility17. All but the most recent studies of block structures are reviewed in References 1-5. (R. J. D. TILLEY)
1. A. D. Wadsley, S. Anderson, in Perspectives in Structural Chemistry, Vol. 3, J. D. Dunitz, J. A. Ibers, eds., Wiley, New York, 1970. 2. J. S. Anderson, in Surface and Defect Properties of Solids, Vol. 1, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1972, p. 1. 3. J. S. Anderson, R. J. D. Tilley, in Surface and Defect Properties of Solids, Vol. 3, M. W. Roberts, J. M. Thomas, eds., Chemical Society, London, 1974, p. 1. 4. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 1, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1972, p. 279.
182
3.10 Formation of Non-stoichiometric Oxides 3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.2 Nonstoichiometric Layer Structure Oxides
5. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 6. J. S. Anderson, D. J. M . Bevan, A. K. Cheetham, R. B. Von Dreele, J. L. Hutchinson, J. Strahle, Proc. R . Soc. London, Ser. A, 346, 139 (1975). 7. A. J. Skarnulis, S. Iijima, J. M. Cowley, Acta Crystallogr., Sect. A, 32, 799 (1976). 8. S. Iijima, S. Kimura, M. Goto, Acta Crystallogr., Sect. A , 29, 632 (1973). 9. S. Iijima, S. Kimura, M. Goto, Acta Crystallogr., Sect. A, 30, 251 (1974). 10. S. Iijima, Acta Crystallogr., Sect. A, 31, 784 (1975). 11. J. S. Anderson, J. L. Hutchison, J. M. Browne, Acta Crystallogr., Sect. A, 32, 670 (1976). 12. T. Kikuchi, M. Goto, J . Solid State Chem., 16, 363 (1976). 13. R. J. D. Tilley, R. P. Williams, Proc. R. SOC.London, Ser, A, 452, 841 (1966). 14. A.-M. Anthony, J. S. Anderson, J. L. Hutchison, J . Solid State Chem., 21, 233 (1977). 15. J. S. Anderson, Chem. Scripta, 14, 129 (1978-1979). 16. E. S. Crawford, J. S. Anderson, Philos. Trans. R . SOC.London, Ser. A, 304, 327 (1982). 17. M. W. Viccary, R. J. D. Tilley, J . Solid State Chem., 104, 131 (1993).
3.10.3.2 NonstoichiometricLayer Structure Oxides Layer structures are formed of polyhedral sheets whose cohesion is ensured by van der Waals forces or hydrogen or ionic bonds'. For oxides these sheets are often two-dimensional, negatively charged layers held together by intercalated cations. This section uses a broader definition: all compounds that can be described as the association of slabs of different structures, as well as intergrowths, are considered as layer structures, even if they are in fact characterized by a three-dimensional network structure. Four major categories of oxides based on fundamental building units and their architectural arrangement are described: (1) layered oxides involving perovskite slabs, including Ruddlesden-Popper phases, high temperature superconducting cuprates, and the Aurivillius and brownmillerite phases; (2) the hexagonal ferrites, p-aluminas, and LixM204(M = Ti, V, Mn) phases based on the spinel structure; (3) intergrowths of the cage oxide A3M8021(A = Ba, K; M = Ti, Nb, Ta) with tunnel structures, A3M6Si4026; and (4) oxides with intercalation structures ranging from vanadium and molybdenum bronzes, which do not exhibit ion exchange properties, to true intercalation oxides such as certain classes of titanates, titanoniobates, or tantalates. Although this section cannot list all the references for all the compounds mentioned, References 1-8 and references therein provide comprehensive detail on each subject. The layer silicates, known for their intercalation properties are described elsewhere. (M. GREENBLATT, B. RAVEAU)
1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge Universty Press, Cambridge, 1997. 4. A. K. Cheetham, P. Day, eds., Solid State Chemistry Compounds, Clarendon Press, Oxford, 1992. 5. K. J. Rao ed., Perspectiaes in Solid State Chemistry, Narosa Publishing House, New Delhi, 1995. 6. J. Klamut, B. W. Veal, B. M. Dabrowski, P. W. Klamut, M. Kazimierski, eds., Recent Developments in High Temperature Superconducticity, Springer-Verlag, Berlin, 1996. 7. A. R. West, Solid State Chemistry and I t s Applications, Wiley, Chichester, 1984. 8. A. D. Wadsley, in Nonstoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
182
3.10 Formation of Non-stoichiometric Oxides 3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.2 Nonstoichiometric Layer Structure Oxides
5. R. J. D. Tilley, in M T P International Reviews of Science, Inorganic Chemistry, Ser. 2, Vol. 10, L. E. J. Roberts, ed., Butterworths, London, 1975, p. 73. 6. J. S. Anderson, D. J. M . Bevan, A. K. Cheetham, R. B. Von Dreele, J. L. Hutchinson, J. Strahle, Proc. R . Soc. London, Ser. A, 346, 139 (1975). 7. A. J. Skarnulis, S. Iijima, J. M. Cowley, Acta Crystallogr., Sect. A, 32, 799 (1976). 8. S. Iijima, S. Kimura, M. Goto, Acta Crystallogr., Sect. A , 29, 632 (1973). 9. S. Iijima, S. Kimura, M. Goto, Acta Crystallogr., Sect. A, 30, 251 (1974). 10. S. Iijima, Acta Crystallogr., Sect. A, 31, 784 (1975). 11. J. S. Anderson, J. L. Hutchison, J. M. Browne, Acta Crystallogr., Sect. A, 32, 670 (1976). 12. T. Kikuchi, M. Goto, J . Solid State Chem., 16, 363 (1976). 13. R. J. D. Tilley, R. P. Williams, Proc. R. SOC.London, Ser, A, 452, 841 (1966). 14. A.-M. Anthony, J. S. Anderson, J. L. Hutchison, J . Solid State Chem., 21, 233 (1977). 15. J. S. Anderson, Chem. Scripta, 14, 129 (1978-1979). 16. E. S. Crawford, J. S. Anderson, Philos. Trans. R . SOC.London, Ser. A, 304, 327 (1982). 17. M. W. Viccary, R. J. D. Tilley, J . Solid State Chem., 104, 131 (1993).
3.10.3.2 NonstoichiometricLayer Structure Oxides Layer structures are formed of polyhedral sheets whose cohesion is ensured by van der Waals forces or hydrogen or ionic bonds'. For oxides these sheets are often two-dimensional, negatively charged layers held together by intercalated cations. This section uses a broader definition: all compounds that can be described as the association of slabs of different structures, as well as intergrowths, are considered as layer structures, even if they are in fact characterized by a three-dimensional network structure. Four major categories of oxides based on fundamental building units and their architectural arrangement are described: (1) layered oxides involving perovskite slabs, including Ruddlesden-Popper phases, high temperature superconducting cuprates, and the Aurivillius and brownmillerite phases; (2) the hexagonal ferrites, p-aluminas, and LixM204(M = Ti, V, Mn) phases based on the spinel structure; (3) intergrowths of the cage oxide A3M8021(A = Ba, K; M = Ti, Nb, Ta) with tunnel structures, A3M6Si4026; and (4) oxides with intercalation structures ranging from vanadium and molybdenum bronzes, which do not exhibit ion exchange properties, to true intercalation oxides such as certain classes of titanates, titanoniobates, or tantalates. Although this section cannot list all the references for all the compounds mentioned, References 1-8 and references therein provide comprehensive detail on each subject. The layer silicates, known for their intercalation properties are described elsewhere. (M. GREENBLATT, B. RAVEAU)
1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge Universty Press, Cambridge, 1997. 4. A. K. Cheetham, P. Day, eds., Solid State Chemistry Compounds, Clarendon Press, Oxford, 1992. 5. K. J. Rao ed., Perspectiaes in Solid State Chemistry, Narosa Publishing House, New Delhi, 1995. 6. J. Klamut, B. W. Veal, B. M. Dabrowski, P. W. Klamut, M. Kazimierski, eds., Recent Developments in High Temperature Superconducticity, Springer-Verlag, Berlin, 1996. 7. A. R. West, Solid State Chemistry and I t s Applications, Wiley, Chichester, 1984. 8. A. D. Wadsley, in Nonstoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.1 lntergrowth of Perovskite with Rock Salt Layers
183
3.10.3.2.1 Layered Oxides Based on the Perovskite Structure
3.10.3.2.1.1 lntergrowth of Perovskite with Rock Salt Layers: Ruddlesden-Popper Phases. The structure of cubic perovskite SrTi03 and the rock salt structure of SrO are characterized by identical (001) planes with composition “SrO.” The two structures can be juxtaposed, leading to a series of intergrowth phases of general formula (SrTi03),Sr0 in which multiple perovskite layers, n octahedra thick, alternate with single “SrO” rock salt layers as shown in Figure 1 for the first three membes of the series Sr2Ti04,( n = 1; K2NIF4-typestructure (see Fig. la), Sr3Ti207,( n = 2; see Fig. lb) and Sr4Ti3010, ( n = 3; see Fig. lc). Theoretically, members of the series, Srn+lTin03n+l, referred to as Ruddlesden-Poppper (RP) phases’, can exist with n = 1 to n = x (the perovskite, SrTi03; see Fig. Id). However as n increases, disorder in the stacks increases. Nonintegral n members can also be expected; for example, n = 1.5 is the intergrowth of the n = 1 and n = 2 members. This type of intergrowth is not limited to the titanates. Several series of RP phases, (AM(&), AO(A,+ 1Mn03,+I ) , similar to the Sr,+ 1Tin03*+1 system, are known with A = Ca, Sr: Eu(II),and M = Mn’, Ti’; A = Sr and M = V3, Co4, Ru5, Fe6; A = Ba and M = Pb’, Bi8 and A = La (and other rare earth ions) and M = Mn9, Nilo. These materials are currently under intense investigation for their interesting low-dimensional physical properties, including metal-to-insulator transition, charge-density wave state, giant or colossal magnetoresistance, and superconductivity,
(b)
n = 2
n - 3
n -
m
Figure 1. The idealized structure of A n + l M n 0 3 n LRP 1 phases; small and medium solid circles refer to M and A respectively; open circle corresponds to oxygen ions. (After Ref. 10.)
184
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
and because of their structural and electronic similarities to the high temperature superconducting cuprates discovered in the last decade’ 12. ‘3
(M. GREENBLATT, B. RAVEAU)
1. S. N. Ruddlesden, P. Popper, Acta Crystall., 10, 538 (1957); 11, 54 (1958). 2. J. B. MacChesney, H. J. Williams, J. F. Potter, R. C. Sherwood, Phys. Rec., 164, 779 (1967). 3. J. G. Lee, K. V. Ramanujachary, M. Greenblatt, J . Solid State Chem., 118, 292 (1995). 4. S. E. Dann, M. T. Weller, J . Solid State Chem., 115, 499 (1995). 5. M. Itoh, M. Shikano, T. Shimura, Phys. Rev., 51B, 16432, (1995); R. J. Cava, H. W. Zandbergen, J. J. Krajewski, W. F. Peck, Jr., B. Batlogg, S. Carter, R. M. Fleming, 0.Zhou, L. W. Rupp, Jr., J . Solid State Chem., 116, 141 (1995). 6. S. E. Dann, M. T. Weller, D. B. Currie, J . Solid State Chem., 97, 179 (1992); P. Adler, A. F. Goncharov, K. Syassen, Hyperjne Interactions, 95,71 (1995);P. Adler, J . Solid State Chem., 130, 129 (1997). 7. L. F. Mattheiss, Phys. Rel;., B, 42, 359 (1990). 8. R. J. Cava, H. T. Siegrist, W. F. Peck, Jr., J. J. Krajewski, B. Batlogg, J. Rosamilia, Phys. Rev. B, 44, 9746 (1991). 9. See, e.g., C. N. R. Rao, A. K. Cheetham, R. Mahesh, Chem. Mater., 8,2421 (1996); R. Sheshadri, C. Martin, A. Maignan, M. Hervieu, B. Raveau, C. N. R. Rao, J . Mater. Chem., 6, 1585 (1996)
and references therein.
10. M. Greenblatt, Curr. Opinion Solid State Chem. Mater. Sci, 2, 174 (1997). 11. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 12. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997.
3.10.3.2.1.2 High Temperature Superconducting Cuprates. Intergrowth of Oxygen-Deficient Perovskites with Rock Salt Layers in the Layer Cuprates. The multinary cuprates comprise another important RP-type series. High temperature superconductivity (T, 35-40K) was first observed in 1986 in Laz-,A,Cu04 (A = Ca, Sr, Ba)’. Bednorz and Miiller’ received the Nobel Prize in Physics for this work in 1987. The enormous interest and technological importance of these materials led to intense investigations of the cuprates worldwide. Since then, many new high temperature superconducting cuprates (HTSC) have been discovered. These materials all have layered structures, and all can be described in terms of related perovskite- and rock salt- or fluorite-type intergrowth structures. The ordered creation of 0 vacancies in the perovskite layers of the (ACu03-,),(AO), intergrowth leads to a large family of cuprates known for their superconducting properties at high temperature^^.^. The (ACu03-,),(AO), compounds can be synthesized because of Cu’s ability to adopt pyramidal, square-planar, and other coordinations. Reported members of this series are listed in Table 1, where [m,n] represents a member of the series with m perovskitic Cu layers and n rock salt [ A 0 l m layers. The m = 1 members correspond to single octahedral layer intergrown with single ( n = l), as in La2Cu04, or double ( n = 2) T1Ba2Cu05,or triple ( n = 3) as in Tl2Ba2CuO6or Bi2SrzCu06 rock salt layers (Fig. 1). The m = 2 members are characterized by double-pyramidal Cu layers, built from the perovskite, by elimination of rows of 0 atoms along a crystallographic direction (Fig. 2). They differ only in the thickness of the rock salt layer, which is single (n = 1) in LaSrCaCu206(Fig. 2a), double ( n = 2) in T1Ba2CaCu20, or HgBa2CaCu2o6 (Fig. 2b), and triple (n = 3) in T1,Ba2CaCu208 (Fig. 2c). Elimination of rows of oxygens in the triple perovskite layers leads to triple Cu layers, built from one layer of cornersharing square-planar C u 0 4 groups, sandwiched between two pyramidal Cu-0 layers as in T1Ba2Ca2Cu309 and HgBa2Ca2Cu308 with double (n = 2; Fig. 3a) and
-
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
184
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
and because of their structural and electronic similarities to the high temperature superconducting cuprates discovered in the last decade’ 12. ‘3
(M. GREENBLATT, B. RAVEAU)
1. S. N. Ruddlesden, P. Popper, Acta Crystall., 10, 538 (1957); 11, 54 (1958). 2. J. B. MacChesney, H. J. Williams, J. F. Potter, R. C. Sherwood, Phys. Rec., 164, 779 (1967). 3. J. G. Lee, K. V. Ramanujachary, M. Greenblatt, J . Solid State Chem., 118, 292 (1995). 4. S. E. Dann, M. T. Weller, J . Solid State Chem., 115, 499 (1995). 5. M. Itoh, M. Shikano, T. Shimura, Phys. Rev., 51B, 16432, (1995); R. J. Cava, H. W. Zandbergen, J. J. Krajewski, W. F. Peck, Jr., B. Batlogg, S. Carter, R. M. Fleming, 0.Zhou, L. W. Rupp, Jr., J . Solid State Chem., 116, 141 (1995). 6. S. E. Dann, M. T. Weller, D. B. Currie, J . Solid State Chem., 97, 179 (1992); P. Adler, A. F. Goncharov, K. Syassen, Hyperjne Interactions, 95,71 (1995);P. Adler, J . Solid State Chem., 130, 129 (1997). 7. L. F. Mattheiss, Phys. Rel;., B, 42, 359 (1990). 8. R. J. Cava, H. T. Siegrist, W. F. Peck, Jr., J. J. Krajewski, B. Batlogg, J. Rosamilia, Phys. Rev. B, 44, 9746 (1991). 9. See, e.g., C. N. R. Rao, A. K. Cheetham, R. Mahesh, Chem. Mater., 8,2421 (1996); R. Sheshadri, C. Martin, A. Maignan, M. Hervieu, B. Raveau, C. N. R. Rao, J . Mater. Chem., 6, 1585 (1996)
and references therein.
10. M. Greenblatt, Curr. Opinion Solid State Chem. Mater. Sci, 2, 174 (1997). 11. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 12. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997.
3.10.3.2.1.2 High Temperature Superconducting Cuprates. Intergrowth of Oxygen-Deficient Perovskites with Rock Salt Layers in the Layer Cuprates. The multinary cuprates comprise another important RP-type series. High temperature superconductivity (T, 35-40K) was first observed in 1986 in Laz-,A,Cu04 (A = Ca, Sr, Ba)’. Bednorz and Miiller’ received the Nobel Prize in Physics for this work in 1987. The enormous interest and technological importance of these materials led to intense investigations of the cuprates worldwide. Since then, many new high temperature superconducting cuprates (HTSC) have been discovered. These materials all have layered structures, and all can be described in terms of related perovskite- and rock salt- or fluorite-type intergrowth structures. The ordered creation of 0 vacancies in the perovskite layers of the (ACu03-,),(AO), intergrowth leads to a large family of cuprates known for their superconducting properties at high temperature^^.^. The (ACu03-,),(AO), compounds can be synthesized because of Cu’s ability to adopt pyramidal, square-planar, and other coordinations. Reported members of this series are listed in Table 1, where [m,n] represents a member of the series with m perovskitic Cu layers and n rock salt [ A 0 l m layers. The m = 1 members correspond to single octahedral layer intergrown with single ( n = l), as in La2Cu04, or double ( n = 2) T1Ba2Cu05,or triple ( n = 3) as in Tl2Ba2CuO6or Bi2SrzCu06 rock salt layers (Fig. 1). The m = 2 members are characterized by double-pyramidal Cu layers, built from the perovskite, by elimination of rows of 0 atoms along a crystallographic direction (Fig. 2). They differ only in the thickness of the rock salt layer, which is single (n = 1) in LaSrCaCu206(Fig. 2a), double ( n = 2) in T1Ba2CaCu20, or HgBa2CaCu2o6 (Fig. 2b), and triple (n = 3) in T1,Ba2CaCu208 (Fig. 2c). Elimination of rows of oxygens in the triple perovskite layers leads to triple Cu layers, built from one layer of cornersharing square-planar C u 0 4 groups, sandwiched between two pyramidal Cu-0 layers as in T1Ba2Ca2Cu309 and HgBa2Ca2Cu308 with double (n = 2; Fig. 3a) and
-
3.10.3.2 Nonstoichiornetric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
185
TABLE1. SUPERCONDUCTING LAYERED CUPRATES [m,n] m n
1
1
[1,11 La2-,A,Cu04 La2Cu04 (A = Ca, Sr, Ba) T, % 3 5 4 0 K
[3>11 PbBaYSrCu30e T, = 50K
2
[L21 P>21 T1Ba2CaCu,0,-6 TIo 5Pbo5Sr2Cu05-b T, = 40K T, % 6 0 K TI1~ . P r , S r , ~ , P r , C u 0 5 ~ 6 T1Sr2CaCu2O7 T, = 40K T, % 50K Pbl -,M,Sr,Ca, -,Y,CU,O,-~ HgBa2CuOaid T, = 9 4 K (M = Sr, Ca, Cd, Gd, Cu, ) T, = 2&80 K TIo ,Pbo sSr2C aCu207-~ 7, % 7 M 0 K
[3,21 [4>21 T1Ba2Ca2Cu309 T1Ba2Ca3Cu40, T, % 108 K T, % 120K Tlo ,Pbo 5Sr2Ca2Cu309 T, % 120K HgBa2Ca2Cu308 T , % 133 K
3
L31 T1,Ba2Cu06 *
~ 231, T1,Ba2CaCu208
[3,31 T12Ba2Ca2Cu3010
T , = 3&92 K Bi,Sr,CuO, T , % 10-22 K
T, % 105K Bi2-xSr2-xCaCu208+ d T, 4 8 5 K Bi, -.Pb,Sr2Ca, -.Y,Cu208 TC%85K+N.S.
T , % 125-130K T, % 115K Bi2 -xPbxSr2CaZCu3010 T, % llOK
2
3
4
[4>11
[4,31 T12Ba2Ca3Cu4012
cu
Ba,~n
0 0 0
0 0
0
0
T'*Bi
0 0 0 0 0 0 0
Ti 8 a, ~ n
cu ~
0
0
0
~
0
~
0 0 0 0 0 0 0
Figure 1. Schematic structures of (a) BilSrzCuOd and T1,BazCu06 and (b) TlBa2-,Ln,Cu05 (After Ref. 4.)
3.10.3.2 NonstoichiometricLayer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature SuperconductingCuprates
186
O
0
0
0
O
O
O
Q
O
TI
0
0
O 0
O
Q
O
O
O
O
O
0
cu
cu 6
0
O
O
O
O
@
0
0
0
0
0
0
0
(c)
Figure 2. Schematic structure of the m = 2 cuprates (ACu0,-,),(AO),: (a) LaSrCaCu206,(b) T1BazCaCu20,, and (c) TlzBazCaCuzOBor Bi2Sr2CaCuz08.(After Ref. 4.)
187
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
cu O O B O Q O Q
O
Q
O
O
O
Q
O
.... .... (b)
Figure 3. Schematic structure of the m = 3 cuprates (ACuO,-.), (AO),: (a) T1Ba2Ca,Cu30, and (b) T12Ba2Ca2Cu,0,, or Bi2Sr2CazCu3010. (After Ref. 4.)
Figure 4. Schematic structure of Sro.ljCao,sj C u 0 2 . (After Ref. 4.)
188
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
T12BazCazCu3010 and BizSrZCazCu3Ol0triple rock salt layers ( n = 3; Fig. 3b). Further increase in the number of Cu layers ( n > 3) leads to insertion of additional square-planar Cu-0 layers between the square-pyramidal layers as in T1Ba2Ca3Cu401 and HgBaZCa3Cu4Ol0(with n = 2) and T12Ba2Ca3Cu,012 (with n = 3). In general, for a given series, the transition temperature to superconductivity (T,) increases with the number of Cu layers up to m = 3 and thereafter decreases with increasing m. For n = m , one should obtain an 0-deficient perovskite built up of [CuOzlm layers
I
.Cu
! I
0 OX
Figure 5. (a) The structure of SrzCu03,which can be deduced from (b), the L a 2 C u 0 i type structure by eliminating alternate rows of oxygen atoms along b. (After Ref. 8.)
3.10.3.2 NonstoichiometricLayer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
n"
cu
n
189
V
2
cu 1
t C
0
"
Figure 6. Structure of LnBazCu307showing the corner-sharing C u 0 5 pyramids and CuO, square-planar groups as well as the CuOz sticks. (a) The 92K orthorhombic 4 . The superconductor YBa2Cu307.(b) The tetragonal semiconductor Y B a Z C ~ 3 0 6 .(c) insulating tetragonal cuprate YBa2Cu306.(After Ref. 4.)
190
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.2 High Temperature Superconducting Cuprates
of square-planar groups only, interleaved with Ca2+ ion^.^-^ This is the case for Sro IsCao.s5Cu02(Fig. 4). Sr2Cu03 (or C a 2 C u 0 3 ) with an orthorhombic unit cell (a z ap, b z 3.5, and c z 12.7..&;ap is the perovskitic unit cell), which has been made superconducting by appropriate substitutions, is an intergrowth of an 0-deficient perovskite layer with a SrO rock salt layer. The S r 2 C u 0 3 structure is closely related to that of L a 2 C u 0 4 and is derived from the latter by eliminating alternate rows of 0 atoms along b in the perovskite layer. This leads to formation of [CuO,], rows of corner-sharing C u 0 4 groups running along the a axis; these rows form layers parallel to (001) as shown in Figure 5. The structure of YBa2Cu30, (often referred to as the “123” phase) also derives from the A B 0 3 perovskites by elimination of rows of 0 atoms parallel to the [OlO] direction at z = 0 and z = 1/2 in the orthorhombic unit cell (a z ap, b z ap, c 2 3a,) and an ordered arrangement of Ln3+ and Ba2+ ions in the A sites along the c direction (see Fig. 6a). The structure is made up of triple [Cu3071Cclayers of corner-sharing polyhedra, parallel to [OOl], held together by yttrium cations. Each [CU307], layer consists of two sheets of corner-sharing C u 0 5 square pyramids connected to each other through [Cu02], rows of corner-sharing C u 0 4 square-planar groups. The [Cu02], rows run along b. The structure is therefore often described as an association of Cu-0 chains and pyramidal Cu-0 layers. The Cu-0 apical distance is close to 2.3 A, significantly larger than the equatorial 0 - 0 distances (1.92-1.96 A), showing the tendency of Cu to adopt a square-planar coordination within the layers. The two-dimensional character of this structure and the associated mixed valency of Cu(II)/Cu(III) is at the origin of the high critical temperature of 92K for this superconductor. Cuprates of all other lanthanides (Ln), LnBa2Cu307exhibit the same structure and similar properties, except those of Ce and Tb, which have not been prepared so far. YBa2Cu307is nonstoichiometric in 0,and phases with 0 stoichiometry of 6 to 7 can be obtained by various heat treatments. For example, heating the sample in air at 1070 K yields a tetragonal, nonsuperconducting YBa2Cu306 (see Fig. 6b); the tetragonal YBa2Cu306phase is obtained by heating the orthorhombic (123) or the Y B a 2 C ~ 3 0 6 . 4 tetragonal phase in vacuum at 870 K (Fig. 6c). The 0-deficient tetragonal nonsuperconducting compounds are identical in structure to YBa2Cu307,except that in the 6.4 phase there is disordering of oxygens about the square-planar coppers (along x, y , and z ) such that they become 0 deficient octahedra ( C u 0 6 with the basal corners less than half-occupied); in YBa2Cu30athe chain C u atoms become two-coordinate with 0 along b, with the mixed valency C U ( I ) / C U ( I I ) ~ . ~ ~ * , ~ .
-
-
(M. GREENBLATT, B. RAVEAU)
1. C. Michel, B. Raveau, Rev. Chim. Miner., 21, 407 (1984). 2. J. G. Bednorz, K. A. Muller, 2. Phys., 864, 189 (1986). 3. J. Klamut, B. W. Veal, B. M. Dabrowski, P. W. Klamut, M. Kazimierski, eds., Recent Deuelopments in High Temperature Supercondueticity, Springer-Verlag,Berlin, 1996. 4. B. Raveau, C. Michel, H. Hervieu, D. Groult, Crystal Chemistry of High T, Superconducting Oxides, Springer-Verlag,Berlin, 1991. 5. A. M. Hermann, J. V. Yakhmi, eds., Thallium-Based High-Temperature Superconductors, Dekker, New York, 1994. 6. H. Maeda, K. Togano, eds., Bismuth-Based High-Temperature Superconductors, Dekker, New York, 1996.
7 . G. Van Tendeloo, C. Chaillout, J. J. Capponi, M. Marezio, E. V. Antipov, Physica C, 223, 219
(1994).
3.10.3.2 Nonstoichiometric Layer Structure Oxides 191 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.3 lntergrowth of Perovskite with i‘Bip02’’Layers: Aurivillius Phases 8. B. Raveau, Proc. Indian Natl. Sci. Acad., 52A, 67 (1986). 9. C. N. R. Rao, ed., Chernistrj of High Temperature Superconductors, World Scientific, Singapore, 1991.
3.10.3.2.1.3 lntergrowth of Perovskite with “Bi,O,” Layers: Aurivillius Phases’. These complex bismuth oxides have the general formula (Biz0,)2+(A,- 1Bn03nwhere A = K, Ca, Sr, Ba, Pb, Bi and B = Ti, V, Nb, Mo, Ta, W. They are prepared by heating appropriate mixtures of the corresponding oxides. These compounds are of interest because of their ferroelectric’ and oxide ion conducting properties3. The structure forms from the perovskite-rock salt (AM03),,A 0 intergrowths by replacement of the A 0 slabs by (Bi202)’+ sheets; since, however, the different sheets are not directly connected, these intergrowths can be regarded as true sheet structures formed by the stacking of infinite two-dimensional [A,- 1 B n 0 3 n J+m anions and [Bi,O,], cations along [OOl] (Fig. 1). The [Bi202], layers are built up of edge-sharing BiO, pyramids. This unique coordination of Bi(II1) is due to its 6s’ lone pair electrons oriented along the c crystallographic direction. The thickness of the perovskite layers along c is determined by n, which characterizes the number of ReO?-type - - _ layers stacked between two successive layers of [Bi,Oz],. (M. GREENBLATT, B. RAVEAU)
Figure 1. Structure of the Aurivillius phases (Bi202)’+(An-1Bn03n+1)2-. In the layer of edge-sharing B i 0 4 pyramids, the 0 atoms sit in the basal plane, whereas the apical site is occupied by Bi. The M 0 6 octahedra (hatched) form (a) single layers (n = 1) as in Bi,MoO,, (b) double layers ( n = 2) as in Bi2SrNb209,or (c) triple layers ( n = 3) as in Bi,Ti3012. (After Ref. 4.) 1. 2. 3. 4.
B. Aurivillius, Ark. Kent., 1, 463 (1949); 1, 499 (1949). E. C. Subbarao. d. Phjs. Chem. Solids, 23, 665 (1962). K. R. Kendall, C. Navas, J. K. Thomas, H.-C. zur Loye, Chem. Muter., 8, 642 (1996). A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 191 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.3 lntergrowth of Perovskite with i‘Bip02’’Layers: Aurivillius Phases 8. B. Raveau, Proc. Indian Natl. Sci. Acad., 52A, 67 (1986). 9. C. N. R. Rao, ed., Chernistrj of High Temperature Superconductors, World Scientific, Singapore, 1991.
3.10.3.2.1.3 lntergrowth of Perovskite with “Bi,O,” Layers: Aurivillius Phases’. These complex bismuth oxides have the general formula (Biz0,)2+(A,- 1Bn03nwhere A = K, Ca, Sr, Ba, Pb, Bi and B = Ti, V, Nb, Mo, Ta, W. They are prepared by heating appropriate mixtures of the corresponding oxides. These compounds are of interest because of their ferroelectric’ and oxide ion conducting properties3. The structure forms from the perovskite-rock salt (AM03),,A 0 intergrowths by replacement of the A 0 slabs by (Bi202)’+ sheets; since, however, the different sheets are not directly connected, these intergrowths can be regarded as true sheet structures formed by the stacking of infinite two-dimensional [A,- 1 B n 0 3 n J+m anions and [Bi,O,], cations along [OOl] (Fig. 1). The [Bi202], layers are built up of edge-sharing BiO, pyramids. This unique coordination of Bi(II1) is due to its 6s’ lone pair electrons oriented along the c crystallographic direction. The thickness of the perovskite layers along c is determined by n, which characterizes the number of ReO?-type - - _ layers stacked between two successive layers of [Bi,Oz],. (M. GREENBLATT, B. RAVEAU)
Figure 1. Structure of the Aurivillius phases (Bi202)’+(An-1Bn03n+1)2-. In the layer of edge-sharing B i 0 4 pyramids, the 0 atoms sit in the basal plane, whereas the apical site is occupied by Bi. The M 0 6 octahedra (hatched) form (a) single layers (n = 1) as in Bi,MoO,, (b) double layers ( n = 2) as in Bi2SrNb209,or (c) triple layers ( n = 3) as in Bi,Ti3012. (After Ref. 4.) 1. 2. 3. 4.
B. Aurivillius, Ark. Kent., 1, 463 (1949); 1, 499 (1949). E. C. Subbarao. d. Phjs. Chem. Solids, 23, 665 (1962). K. R. Kendall, C. Navas, J. K. Thomas, H.-C. zur Loye, Chem. Muter., 8, 642 (1996). A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
192
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.4 Brownmillerite Family: (AM03),AM02
3.10.3.2.1.4 Brownmillerite Family: (AM03),AM02. These phases, 0-deficient perovskites with an ordered arrangement of 0 vacancies in the [MO,], octahedral framework, are represented by the general formula (AMO,),. A M 0 2 . The frame1, is formed from multiple stoichiometric perovskite layers work structure M,+ that are n octahedra thick, linked by single layers of M 0 4 tetrahedra (Fig. 1 ) ' ~ ~ . The M 0 2 tetrahedral layers are derived from the perovskite lattice by creation of rows of 0 vacancies along the [llO] direction of the perovskite cubic cell in such a way that one 0-deficient row alternates with one fully occupied row. The first member of this series (n = l), with A = Ca and M = Fe, is the well-known brownmillerite CazFe20, (Fig. 1). This structure is also observed for CazFeA105, Ca2FeCo0,, and SrzCozO, (high temperature form), where the transition metals and A1 occupy the tetrahedral sites of the brownmillerite structure. In the n = co, SrFeO, - x phase, Fe is mixed valent [Fe(III)/Fe(IV)] and occupies both the tetrahedral and octahedral sites. More complex structures with nonintegral values of n can form by intergrowth of two integral n members; for example, Ca4YFe5013,Ca,Fe,013 (n = lS), and Ca,YFe6TiO18 ( n = 1.33) represent the ordered intergrowth of n = 1 and n = 2 members, where single [FeO,],, layers alternate with multiple [M03], octahedral layers of different thickness (Fig. 2),. (M. GREENBLATT, B. RAVEAU)
Figure 1. Schematic structure of the brownmillerite derived phases (AMO3)AMO2: (a) n = 1 hypothetical structure of C a 2 F e 2 0 5(b) , n' = 1 actual structure of Ca,Fe20,, (c) n = 2, and (d) n = 3. The M 0 6 octahedra (lozenge shaped) and the M 0 4 tetrahedra (triangles), which are viewed along the (1 10) direction of the perovskite, form rows at two levels alternately (hatched and open polyhedra). (After Refs. 1, 2.)
193 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.5 Titanates and Niobates, A,M,O3,+, and Molybdates, Cs2Mon03,,+,
Figure 2. Schematic structures of (a) Ca,YFeSO1, ( n = 1.5) and (b) Ca7Fe,TiO18 ( n = 1.33). For n = 1.5, the double layers of FeOd octahedra (lozenges) alternate with the single layers of FeO, tetrahedra (triangles). For n = 1.33, single layers of FeO, tetrahedra (triangles) are stacked with double and single layers of Fe(Ti)06 octahedra alternately (lozenges). (After Ref. 3.) 1. B. Raveau, Proc. Indian Natl. Sci. Acad., 52A, 67 (1986). 2. J. C. Grenier, J. Darriet, M. Pouchard, P. Hagenmuller, Mater. Res. Bull., 11, 1219 (1976). 3. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995.
3.10.3.2.1.5 Titanates and Niobates, AnM,,03,,+, and Molybdates, Cs2Mon03,,+, Derived from the Perovskite Structure. Oxides of formula A n M n 0 3 n +form 2 a large family of compounds with A = alkaline earth and/or lanthanide ion and M = Ti or Nb. Various members of this series are found in the A2Nb2O7/CaTiO, (A = Ca, Sr) and Ln2Ti20,/CaTi03 (Ln = La, Nd) systems"'. The structure of these oxides consists of anionic layers of [Mn03n+2]n' (2n < n' < 3n) held together by the A'+ or A3+ ions (Fig. 1). These octahedral layers have a distorted perovskite configuration leading to diamond-shaped tunnels along the a direction of the orthorhombic unit cell, where the A cations are located. The cations have irregular coordination ranging from 7 to 12, with the cations located between layers having coordination numbers lower than those
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 193 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.5 Titanates and Niobates, A,M,O3,+, and Molybdates, Cs2Mon03,,+,
Figure 2. Schematic structures of (a) Ca,YFeSO1, ( n = 1.5) and (b) Ca7Fe,TiO18 ( n = 1.33). For n = 1.5, the double layers of FeOd octahedra (lozenges) alternate with the single layers of FeO, tetrahedra (triangles). For n = 1.33, single layers of FeO, tetrahedra (triangles) are stacked with double and single layers of Fe(Ti)06 octahedra alternately (lozenges). (After Ref. 3.) 1. B. Raveau, Proc. Indian Natl. Sci. Acad., 52A, 67 (1986). 2. J. C. Grenier, J. Darriet, M. Pouchard, P. Hagenmuller, Mater. Res. Bull., 11, 1219 (1976). 3. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995.
3.10.3.2.1.5 Titanates and Niobates, AnM,,03,,+, and Molybdates, Cs2Mon03,,+, Derived from the Perovskite Structure. Oxides of formula A n M n 0 3 n +form 2 a large family of compounds with A = alkaline earth and/or lanthanide ion and M = Ti or Nb. Various members of this series are found in the A2Nb2O7/CaTiO, (A = Ca, Sr) and Ln2Ti20,/CaTi03 (Ln = La, Nd) systems"'. The structure of these oxides consists of anionic layers of [Mn03n+2]n' (2n < n' < 3n) held together by the A'+ or A3+ ions (Fig. 1). These octahedral layers have a distorted perovskite configuration leading to diamond-shaped tunnels along the a direction of the orthorhombic unit cell, where the A cations are located. The cations have irregular coordination ranging from 7 to 12, with the cations located between layers having coordination numbers lower than those
194 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.1 Layered Oxides Based on the Perovskite Structure 3.10.3.2.1.5 Titanates and Niobates, A,M,O,,+, and Molybdates,C S , M O ~ O ~ ~ ~ ,
Figure 1. Layered perovskites, A n M n 0 3 n + 2(a) : n Refs. 1 and 2.)
= 4,
(b) n
=
5 , and (c) n = 6. (After
located in the perovskite. As for the previously described oxides, the integer n corresponds to the number of M 0 6 octahedra, which determines the width of the perovskite slabs. Nonintegral n values lead to the formation of intergrowths between members of integral n. Cs2Mo5OI6 and C S ~ M O , Oare ~ ~ examples of the cesium molybdates, C S ~ M O , , O ~Their ~ + structure consists of octahedral [M,03, + 1]2 - infinite layers held together by the CS' ions. The layers consists of Re0,-type slabs, n octahedra wide. In the (010) planes the Re0,-type ribbons share octahedral edges, forming rock salt-type ribbons. A related series of oxides, A'[A,- 1M,03,+ J,has been r e p ~ r t e d ~ . ~ . (M. GREENBLATT, B. RAVEAU) 1. M. Nanot, F. Queyroux, J. C. Gilles, A. Carpy, J. Galy, J . Solid Stare Chem., 11, 272 (1974). 2. B. Raveau, Proc. Indian Natl. Sci. Acad., 52A, 67 (1986). 3. B. M. Gatehouse. M. C. Nesbit, J . Solid Stare Chem., 33, 153 (1980); B. M. Gatehouse, in Solid State Chemistry, R. S. Roth, S. J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC; 1972. p. 15; B. M. Gatehouse, J . Less Cornwon Met., 36,53 (1974). 4. M. Dion, M. Ganne, M. Tournoux. Muter. Res. Bull., 16, 1429 (1981). 5. A. J. Jacobson, J. W. Johnson, J. T. Lewandowski, Inorg. Chem., 24, 3727 (1985).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.2 Oxides Based on the Spinel Structure; Hexagonal Ferrites 3.10.3.2.2.1 Hexagonal Ferrites ~~
195
~
3.10.3.2.2 Oxides Based o n the Spinel Structure; Hexagonal Ferrites,
p-Alumina Oxide Types, and Li,M204 (M =Ti, V, Mn)1-3
3.10.3.2.2.1 Hexagonal Ferrites. The hexagonal ferrites, synthesized from reactions in the systems AO-Fe203-MO (A = Ba, Pb, Sr; M = Mg, Fe, Co, Ni, Zn), have important industrial applications because of their magnetic properties. Many coupled substitutions, such as the replacement of M cation by Li+/Fe3' and Lic/Sn4' are possible without altering the structure. More than 60 Ba-ferrites are known. The structure of the hexagonal ferrites ( a 6 A) results from alternate stacking of closepacked 0 slabs: denoted as 0 4 , and the A-substituted anionic layers, A 0 3 (Figure l)4. Close packing of these anionic layers yields structural units of four types: the S units are closely related to the spinel structure (thus represented by S) corresponding to a facecentered cubic stacking of the oxygen ions (abc) with the composition B608, where B = M + Fe (e.g., MFe204). In these spinel slabs, the Fe atoms are in octahedral and tetrahedral positions. The R unit (Fig. l),corresponding to the formula B6BaOl 1, is built up of two O4 oxygen planes, in hexagonal close-packing (aba) on both sides of the Ba03 plane. The T units (Fig. l), with composition B&a2014 contain two successive Ba03 layers bounded by two 0 planes. In the S, R, and T units, the octahedral and tetrahedral sites are occupied by small cations. The Q (Fig. 1) and T units bear a close relationship, but differ in the type of stacking [(abc) and (ab), respectively), as shown in Figure 11. The hexagonal barium ferrites are built up from these four different types of unit along c. The general formula of these ferrites is [B608]: [B6BaOl ,!]I [BsBa2014];, [B7Ba2Ol4IQ,where n, n', n" are n"' are integers. The stacking sequences are denoted by S, R, T, and Q (S*, R*, T*, and Q* units are obtained from S, R, T and Q units, respectively, by rotation of 180" around the c-axis). The theoretical number of possible sequences of these ferrites is infinite, and many combinations have been observed5. Even in the most complex ferrites: however, certain sequences of stacking are found: BazFe4Os(S), BaFel2019 (M = R, S, R*, S*), and BaM2Fe12022 [Y = (TS)3]. These units show preferences for stacking, giving rise to two main series, M,S and M,Y,. The simplest members of the series are also represented by the letters U, W, X, and Z . Table 1 presents some representative sequences2. Iron can be easily replaced by other trivalent cations in these compounds without changing the structure. The presence of hexagonal close-packed anion layers allows
-
S
R
T
Q
0 cation in octsh*dr8l sit. 0 eatlon in bipyramidal coordinalion 0 cation in IalrahedrJ ~ 1 1 0 .
Figure 1. Schematic drawing of the S, R, T, and Q units of the hexagonal ferrites. (After Ref. 1.)
196
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.2 Oxides Based on the Spinel Structure; Hexagonal Ferrites 3.10.3.2.2.2 The p-Alumina Family
TABLE 1. SEQUENCES IN THE HEXAGONAL FERRITES
accommodation of other close-packed arrangements. This is confirmed by the synthesis of oxides such as BasZn2Ti3Fe12031, which consists of a six-anion-layer Y block alternating with a three-anion-layer hexagonal BaTi03 block. (M. GREENBLATT, B. RAVEAU) 1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997. 4. S. Lacorre, M. Hervieu, B. Raveau, Rec. Inorg. Chem., 6, 195 (1984). 5 . F. Y. Franklin, ed., Fourth International conference on Ferrites, American Ceramic Society, Columbus OH. 1984.
3.10.3.2.2.2 The /%Alumina Family. These compounds, discovered in 1967, have high cationic conductivity’. They have been intensively investigated as solid state electrolytes for the sodium-sulfur battery. In general, the p-aluminas, A l +,MI +X (A = Li’, Na’, K + , Rb’, Tl+,Cs*,Ag’, NH; or H,O+; M = Al, Fe, or Ga) are layered nonstoichiometric compounds. For sodium p-alumina, x is typically 0.20. Its hexagonal structure (Fig. 1) consists of two close-packed spinel blocks four 0 atoms thick, lying along the c axis; the two blocks are separated by a mirror plane, in which the density of 0 atoms is only one-fourth that in the spinel blocks. These mirror planes contain mobile Na’ ions. Na’ ion transport is essentially two-dimensional.2 Nonstoichiometry arises from the possible accommodation of variable quantities of oxygen and sodium ions in the conducting planes3. Sodium @”-aluminahas the general formula Nal +xAll -xM,017; M is a divalent cation such as ME’+, Ni2+, or Zn2+. A typical p”-alumina composition is Nal +,All -xMg,0174.The p’-aluminas have a similar structure to p-aluminas, except that there are three spinel blocks in Pf5. The p” phases contain more Na’ ions than the p phases; therefore they exhibit greater ionic conductivity. p”’ and p’”-aluminas also are observed in the AI2O3-Na20-Mg0 system. Their structures are, respectively, similar to p and /3”, but with spinel-like blocks containing six close-packed 0 layers instead of four. Sodium 0- and p”- aluminas exhibit fascinating ion exchange chemistry6. The Na’ ions can be replaced by a large variety of monovalent cations (e.g., K’, Rb’, Tl’, Cs’, Ag’, Cu’), divalent cations, including the alkaline earth and P b Z f 6 .Even trivalent cation exchange with Eu3+, Nd3+, and Ho3+ have been made; these rare earth-exchanged materials are explored as potential phosphors and lasers7~*. (M. GREENBLATT, B. RAVEAU)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
196
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.2 Oxides Based on the Spinel Structure; Hexagonal Ferrites 3.10.3.2.2.2 The p-Alumina Family
TABLE 1. SEQUENCES IN THE HEXAGONAL FERRITES
accommodation of other close-packed arrangements. This is confirmed by the synthesis of oxides such as BasZn2Ti3Fe12031, which consists of a six-anion-layer Y block alternating with a three-anion-layer hexagonal BaTi03 block. (M. GREENBLATT, B. RAVEAU) 1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997. 4. S. Lacorre, M. Hervieu, B. Raveau, Rec. Inorg. Chem., 6, 195 (1984). 5 . F. Y. Franklin, ed., Fourth International conference on Ferrites, American Ceramic Society, Columbus OH. 1984.
3.10.3.2.2.2 The /%Alumina Family. These compounds, discovered in 1967, have high cationic conductivity’. They have been intensively investigated as solid state electrolytes for the sodium-sulfur battery. In general, the p-aluminas, A l +,MI +X (A = Li’, Na’, K + , Rb’, Tl+,Cs*,Ag’, NH; or H,O+; M = Al, Fe, or Ga) are layered nonstoichiometric compounds. For sodium p-alumina, x is typically 0.20. Its hexagonal structure (Fig. 1) consists of two close-packed spinel blocks four 0 atoms thick, lying along the c axis; the two blocks are separated by a mirror plane, in which the density of 0 atoms is only one-fourth that in the spinel blocks. These mirror planes contain mobile Na’ ions. Na’ ion transport is essentially two-dimensional.2 Nonstoichiometry arises from the possible accommodation of variable quantities of oxygen and sodium ions in the conducting planes3. Sodium @”-aluminahas the general formula Nal +xAll -xM,017; M is a divalent cation such as ME’+, Ni2+, or Zn2+. A typical p”-alumina composition is Nal +,All -xMg,0174.The p’-aluminas have a similar structure to p-aluminas, except that there are three spinel blocks in Pf5. The p” phases contain more Na’ ions than the p phases; therefore they exhibit greater ionic conductivity. p”’ and p’”-aluminas also are observed in the AI2O3-Na20-Mg0 system. Their structures are, respectively, similar to p and /3”, but with spinel-like blocks containing six close-packed 0 layers instead of four. Sodium 0- and p”- aluminas exhibit fascinating ion exchange chemistry6. The Na’ ions can be replaced by a large variety of monovalent cations (e.g., K’, Rb’, Tl’, Cs’, Ag’, Cu’), divalent cations, including the alkaline earth and P b Z f 6 .Even trivalent cation exchange with Eu3+, Nd3+, and Ho3+ have been made; these rare earth-exchanged materials are explored as potential phosphors and lasers7~*. (M. GREENBLATT, B. RAVEAU)
197 3.1 0.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.3 Intergrowths of the Cage Oxide A,M,O,, with a Tunnel Structure
(a)
(b)
Figure 1. Crystal structure and sodium sites in the conduction plane of fi-alumina: (a) unit cell structure and (b) site model of conduction plane. (After Ref. 2.) 1. Y. F. Y. Yao, J. T. Kummer, J . Inorg. Nucl. Chem., 29, 2453 (1967). 2. R. Collongues, J. Thery, J. P. Boilot, in Solid Electrolytes, P. Hagenmuller, ed., Academic Press, New York, 1978, p. 253. 3. For general reviews on ionic conductivity, see: D. F. Shriver, G. C. Farrington, Chem. Eng. News, 63,42 (1985); Ionic Conductors: Encyclopedia ofInorganic Chemistry,Vol. 3, M. Greenblatt, R. B. King, eds., Wiley, New York, 1994, p. 1584. 4. J. L. Briant, G. C. Farrington, J , Solid State Chem., 33, 385 (1980). 5. M. Bettman, C. R. Peters, J . Phys. Chem., 73, 1774 (1969). 6. J. T. Kummer, Prog. Solid State Chem., 7, 141 (1972). 7. B. Dunn, G. C. Farrington, Mater. Res., Bull., 15, 1773 (1980). 8. J. D. Berrie, B. Dunn, Solid State Ionics, 53, 496 (1992).
3.10.3.2.2.3LixM204(M =Ti, V, Mn) Phases. These materials form with the spinel structure and are prepared by conventional solid state reactions from stoichiometric mixtures of the appropriate starting materials in evacuated quartz tubes at high temperatures. LixTi204prepared at high temperature is superconducting'. The LixV204and the Li,Mn204 phases have been investigated as cathode materials for rechargeable solid state lithium batteries2. An excellent review has been published recently on these materials3. (M. GREENBLATT, B. RAVEAU) 1. D. C. Johnson, H. Prakash, W. H. Zachariasen, R. Wiswanathan, Muter. Res. Bull., 8, 777 (1973). 2. P. Strobel, F. Le Cras, M. Anne, J . Solid State Chem., 124, 83 (1997). 3. For a review, see, R. Koksbang, J. Barker, H. Shi, M. Y. Saidi, Solid State lonics, 84, 1 (1996). 3.10.3.2.3 lntergrowths of the Cage Oxide A,M,O,,
with a Tunnel Structure, A,M,Si,O,,l
The intergrowth structure of A3MBOZ1(A = Ba, K; M = Nb, Ta, Ti) is formed from triple files of edge-sharing octahedra connected through single octahedra
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
197 3.1 0.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.3 Intergrowths of the Cage Oxide A,M,O,, with a Tunnel Structure
(a)
(b)
Figure 1. Crystal structure and sodium sites in the conduction plane of fi-alumina: (a) unit cell structure and (b) site model of conduction plane. (After Ref. 2.) 1. Y. F. Y. Yao, J. T. Kummer, J . Inorg. Nucl. Chem., 29, 2453 (1967). 2. R. Collongues, J. Thery, J. P. Boilot, in Solid Electrolytes, P. Hagenmuller, ed., Academic Press, New York, 1978, p. 253. 3. For general reviews on ionic conductivity, see: D. F. Shriver, G. C. Farrington, Chem. Eng. News, 63,42 (1985); Ionic Conductors: Encyclopedia ofInorganic Chemistry,Vol. 3, M. Greenblatt, R. B. King, eds., Wiley, New York, 1994, p. 1584. 4. J. L. Briant, G. C. Farrington, J , Solid State Chem., 33, 385 (1980). 5. M. Bettman, C. R. Peters, J . Phys. Chem., 73, 1774 (1969). 6. J. T. Kummer, Prog. Solid State Chem., 7, 141 (1972). 7. B. Dunn, G. C. Farrington, Mater. Res., Bull., 15, 1773 (1980). 8. J. D. Berrie, B. Dunn, Solid State Ionics, 53, 496 (1992).
3.10.3.2.2.3LixM204(M =Ti, V, Mn) Phases. These materials form with the spinel structure and are prepared by conventional solid state reactions from stoichiometric mixtures of the appropriate starting materials in evacuated quartz tubes at high temperatures. LixTi204prepared at high temperature is superconducting'. The LixV204and the Li,Mn204 phases have been investigated as cathode materials for rechargeable solid state lithium batteries2. An excellent review has been published recently on these materials3. (M. GREENBLATT, B. RAVEAU) 1. D. C. Johnson, H. Prakash, W. H. Zachariasen, R. Wiswanathan, Muter. Res. Bull., 8, 777 (1973). 2. P. Strobel, F. Le Cras, M. Anne, J . Solid State Chem., 124, 83 (1997). 3. For a review, see, R. Koksbang, J. Barker, H. Shi, M. Y. Saidi, Solid State lonics, 84, 1 (1996). 3.10.3.2.3 lntergrowths of the Cage Oxide A,M,O,,
with a Tunnel Structure, A,M,Si,O,,l
The intergrowth structure of A3MBOZ1(A = Ba, K; M = Nb, Ta, Ti) is formed from triple files of edge-sharing octahedra connected through single octahedra
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
197 3.1 0.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.3 Intergrowths of the Cage Oxide A,M,O,, with a Tunnel Structure
(a)
(b)
Figure 1. Crystal structure and sodium sites in the conduction plane of fi-alumina: (a) unit cell structure and (b) site model of conduction plane. (After Ref. 2.) 1. Y. F. Y. Yao, J. T. Kummer, J . Inorg. Nucl. Chem., 29, 2453 (1967). 2. R. Collongues, J. Thery, J. P. Boilot, in Solid Electrolytes, P. Hagenmuller, ed., Academic Press, New York, 1978, p. 253. 3. For general reviews on ionic conductivity, see: D. F. Shriver, G. C. Farrington, Chem. Eng. News, 63,42 (1985); Ionic Conductors: Encyclopedia ofInorganic Chemistry,Vol. 3, M. Greenblatt, R. B. King, eds., Wiley, New York, 1994, p. 1584. 4. J. L. Briant, G. C. Farrington, J , Solid State Chem., 33, 385 (1980). 5. M. Bettman, C. R. Peters, J . Phys. Chem., 73, 1774 (1969). 6. J. T. Kummer, Prog. Solid State Chem., 7, 141 (1972). 7. B. Dunn, G. C. Farrington, Mater. Res., Bull., 15, 1773 (1980). 8. J. D. Berrie, B. Dunn, Solid State Ionics, 53, 496 (1992).
3.10.3.2.2.3LixM204(M =Ti, V, Mn) Phases. These materials form with the spinel structure and are prepared by conventional solid state reactions from stoichiometric mixtures of the appropriate starting materials in evacuated quartz tubes at high temperatures. LixTi204prepared at high temperature is superconducting'. The LixV204and the Li,Mn204 phases have been investigated as cathode materials for rechargeable solid state lithium batteries2. An excellent review has been published recently on these materials3. (M. GREENBLATT, B. RAVEAU) 1. D. C. Johnson, H. Prakash, W. H. Zachariasen, R. Wiswanathan, Muter. Res. Bull., 8, 777 (1973). 2. P. Strobel, F. Le Cras, M. Anne, J . Solid State Chem., 124, 83 (1997). 3. For a review, see, R. Koksbang, J. Barker, H. Shi, M. Y. Saidi, Solid State lonics, 84, 1 (1996). 3.10.3.2.3 lntergrowths of the Cage Oxide A,M,O,,
with a Tunnel Structure, A,M,Si,O,,l
The intergrowth structure of A3MBOZ1(A = Ba, K; M = Nb, Ta, Ti) is formed from triple files of edge-sharing octahedra connected through single octahedra
198
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.3 lntergrowths of the Cage Oxide A3M8O2,with a Tunnel Structure
Figure 1. Structure of A3M8021showing triple files of octahedra connected through single octahedra. (After Ref. 1.)
Figure 2. Structure of A6MI4Si4O4,the first term of the intergrowth, (A3M6Si402& (A3M8021)n.. (After Ref. 1.)
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.1 Vanadium Bronzes
199
(Figure 1). Owing to its similarity to the tunnel structure A&Si4026 (see 3.10.3.3.5.1, Fig. l), a juxtaposition of both structures is possible. A series of intergrowths, (A3M6Si40z6)n(A3M8021)n have thus been synthesized. Besides the single intergrowths corresponding to integral n and n‘ values, multiple intergrowths are also observed for nonintegral n or n’ values (e.g., n = 4.5). Figure 2 corresponds to an intergrowth of n = 4 and n = 5. Figure 2 shows the structure of A6M14Si4047, the first term of this series. (M. GREENBLATT, B. RAVEAU)
1. B. Raveau, Ret. Inorg. Chem., I , 81 (1979). 3.10.3.2.4 Oxides with Intercalation Structures: Layers Built Up of Edge-Sharing Octahedra
3.10.3.2.4.1 Vanadium Bronzes’ -3. The vanadium oxide framework of ternary alkali metal vanadium oxide bronzes bears close structural similarities to the binary vanadium oxides with the same VjO ratio. Prime examples are the layer structures of vanadium bronzes A,Vz05 and Al cxV308,which are synthesized by reduction of Vz05 by a metal, and by reaction of V 2 0 5 on mixtures of vanadate and VOz or V203, respectively. Four layerlike structures have been isolated corresponding to the composition AxV205,SI, x’,7 , and 6, depending on the value of x and the nature of the A ion. Their structure is formed of (V,O,), sheets, between which A ions are inserted. The V z 0 5layers are built from corner- and edge-sharing octahedra for CI and SI’ (Fig. lb-d) and y (Fig. le) and edge-sharing octahedra for the 6 phase. The SI phases, whose structure is closely related to VzOs,are obtained for low x values (x < 0.15) and for monovalent and divalent A ions such as Li’, Na’, Ag’, K’, CU”, C d 2 + ,P b 2 + ,and Zn2’. The x‘ phase, whose structure is similar to x, except that two different bipyramidal sites are available for V, is obtained only for sodium and 0.70 < x < 1. The 6 phase has been synthesized for Ag-rich compositions (0.67 < x < 0.86). More recently new polymorphs of LixVz05,which can be considered to be intercalation compounds, have been prepared at RT by reaction of lithium with V z 0 5 or by treatment of V 2 0 , with LiI in the MeCN4-6. These are of interest as cathode materials for rechargeable Li batteries. Single phases of Li,V205 are observed for x < 0.2 ( x , same as the high temperature phase) 0.3 < x < 0.7 ( E , a new low-temperature phase), and 0.7 < x < 1.0 (8,new low-temperature phase). Similar phases can be obtained electrochemically and by treatment of V 2 0 5with n-butyllithium (n-BuLi) in hexane, although the phase boundaries are slightly different from those observed for the LiI/MeCN reaction. The structure of the new Li,V,O, phases is closely related to that of V205. Above 300’C. these Li,V205 compounds are irreversibly converted to the high temperature bronzes of the same composition. Hydrogen intercalation compounds of VzO, are prepared by electrochemical reduction in acid solution, or by chemical reduction (hydrogen “spillover”) of hydrogen and a noble metal (e.g., P) catalyst6. Hydrogen “spillover” gives an amorphous phase H,V205 with the composition x z 0.38. Electrochemical synthesis with a solid proton conducting electrolyte yields three distinct phases of HxV205: x < 0.5, 1.3 < x < 2.3, and 3.0 < x < 3.8. The structure of H,Vz05 is similar to the corresponding MOO, (see below) phases, indicating the presence of -OH groups when x < 0.5 and -OHz groups for x = 2.56. Although crystalline V z 0 5is layerlike, unlike the van der Waals-bonded hosts such as MOO,, interaction between the layers is sufficient to preclude intercalation of cations
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.1 Vanadium Bronzes
199
(Figure 1). Owing to its similarity to the tunnel structure A&Si4026 (see 3.10.3.3.5.1, Fig. l), a juxtaposition of both structures is possible. A series of intergrowths, (A3M6Si40z6)n(A3M8021)n have thus been synthesized. Besides the single intergrowths corresponding to integral n and n‘ values, multiple intergrowths are also observed for nonintegral n or n’ values (e.g., n = 4.5). Figure 2 corresponds to an intergrowth of n = 4 and n = 5. Figure 2 shows the structure of A6M14Si4047, the first term of this series. (M. GREENBLATT, B. RAVEAU)
1. B. Raveau, Ret. Inorg. Chem., I , 81 (1979). 3.10.3.2.4 Oxides with Intercalation Structures: Layers Built Up of Edge-Sharing Octahedra
3.10.3.2.4.1 Vanadium Bronzes’ -3. The vanadium oxide framework of ternary alkali metal vanadium oxide bronzes bears close structural similarities to the binary vanadium oxides with the same VjO ratio. Prime examples are the layer structures of vanadium bronzes A,Vz05 and Al cxV308,which are synthesized by reduction of Vz05 by a metal, and by reaction of V 2 0 5 on mixtures of vanadate and VOz or V203, respectively. Four layerlike structures have been isolated corresponding to the composition AxV205,SI, x’,7 , and 6, depending on the value of x and the nature of the A ion. Their structure is formed of (V,O,), sheets, between which A ions are inserted. The V z 0 5layers are built from corner- and edge-sharing octahedra for CI and SI’ (Fig. lb-d) and y (Fig. le) and edge-sharing octahedra for the 6 phase. The SI phases, whose structure is closely related to VzOs,are obtained for low x values (x < 0.15) and for monovalent and divalent A ions such as Li’, Na’, Ag’, K’, CU”, C d 2 + ,P b 2 + ,and Zn2’. The x‘ phase, whose structure is similar to x, except that two different bipyramidal sites are available for V, is obtained only for sodium and 0.70 < x < 1. The 6 phase has been synthesized for Ag-rich compositions (0.67 < x < 0.86). More recently new polymorphs of LixVz05,which can be considered to be intercalation compounds, have been prepared at RT by reaction of lithium with V z 0 5 or by treatment of V 2 0 , with LiI in the MeCN4-6. These are of interest as cathode materials for rechargeable Li batteries. Single phases of Li,V205 are observed for x < 0.2 ( x , same as the high temperature phase) 0.3 < x < 0.7 ( E , a new low-temperature phase), and 0.7 < x < 1.0 (8,new low-temperature phase). Similar phases can be obtained electrochemically and by treatment of V 2 0 5with n-butyllithium (n-BuLi) in hexane, although the phase boundaries are slightly different from those observed for the LiI/MeCN reaction. The structure of the new Li,V,O, phases is closely related to that of V205. Above 300’C. these Li,V205 compounds are irreversibly converted to the high temperature bronzes of the same composition. Hydrogen intercalation compounds of VzO, are prepared by electrochemical reduction in acid solution, or by chemical reduction (hydrogen “spillover”) of hydrogen and a noble metal (e.g., P) catalyst6. Hydrogen “spillover” gives an amorphous phase H,V205 with the composition x z 0.38. Electrochemical synthesis with a solid proton conducting electrolyte yields three distinct phases of HxV205: x < 0.5, 1.3 < x < 2.3, and 3.0 < x < 3.8. The structure of H,Vz05 is similar to the corresponding MOO, (see below) phases, indicating the presence of -OH groups when x < 0.5 and -OHz groups for x = 2.56. Although crystalline V z 0 5is layerlike, unlike the van der Waals-bonded hosts such as MOO,, interaction between the layers is sufficient to preclude intercalation of cations
200
3.1 0.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.1 Vanadium Bronzes
Figure 1. V z 0 5 and a-A,V205 bronzes. (a) [V205] cc layers. (b) Ideal octahedral structure. (c) Ideal pyramidal structure equivalent to the octahedral structure. (d) Ideal pyramidal structure after moving apart the V z 0 5 layers from each other, allowing A cations (dots) to be inserted. (e) Structure of the bronze y-Li,V20s, built from V 0 5 pyramids forming layers intercalated with lithium ions (dots). (After Ref. 1.)
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.1 Vanadium Bronzes
201
Figure 2. The Lil +,V308 structure. (After Ref. 9.)
'2'5
V02
(B)
'6'13
Figure 3. Idealized shear representations of vanadium oxides showing the close structural relationship of V 2 0 5 , V02(B),and V6013. larger than Li+ or H'. In contrast, when V 2 0 , is prepared in the gel form, it behaves much like a layered phase in its intercalation chemistry'. A vanadium oxide with true layer structure is Lil +xV308.It is impossible to prepare the parent host [since V(V1) is required], but the bronze itself undergoes ion exchange and solvation reactions similar to the van der Waals intercalation compoundss. The structure of Lil+xV308(Fig. 2 ) is made up of V 3 0 8 layers, composed of distorted edge-sharing octahedra; the sheets are held together by the Li' ions. Analogous
202
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.2 H,MoO,: Hydrogen-IntercalatedCompounds of MOO,
Al +xV308(A = Li, Na, Ag, Cu) and Al +x(V308)2(A = Zn, Mg, Ni, Co) structures are formed of (V308), sheets packing A ions’. The structure of V6013can be seen as arising from a (2,3) shear of ReO, (Fig. 3). This shows how the structures of V2O5, VO,(B), and V6013 are derived from ReO, by successive shears. The three-dimensional structure consists of alternating planes of double and single chains of V 0 6 octahedra. Channels made of tricapped cuboctahedra extend through the structure. Treatment of V6013 with n-BuLi yields intercalation compounds LiXV6Ol3with x = 4 at RT and x = 6 at 50’C. The binary transition metal oxides MO, (e.g., M = Mo, Ru, Os, Ir) with the rutile structure form Li,M02 (with x > 1) insertion compounds. When treated with n-BuLi’’, the rutile phase of V 0 2 does not seem to intercalate significant amounts of Li. However, interacalation occurs readily in a metastable form of V 0 2 , designated as V02(B).The structure of VO,(B) can be considered as a (2,2) shear of Re03. It contains one-dimensional channels of tetracapped cuboctahedral cavities. VO,(B) is essentially the V6013structure without the single chains. Li,VO,(B) with x = 0.5 can be prepared. (M. GREENBLATT, B. RAVEAU) 1. P. Hegenmuller, Prog. Solid State Clzeni.,5, 71 (1971). 2. E. Banks, A. Wold, in Preparatioe Inorganic Chemistry, Vol. 4, W. L. Jolly, ed., New York, 1969, p. 252. 3. A. A. Fotiev, B. L. Volkov, B. K. Kapustkin, Vanadium Bronzes, Academy Nauk, Moscow, 1978 (in Russian). 4. See, for example: D. W. Murphy, in Intercalation Chemistry, M. S . Whittingham, A. J. Jacobson, Academic Press, New York, 1982, p. 563. 5. D. W. Murphy, P. A. Christian, F. J. DiSalvo, J. V. Waszczak, Inorg. Chem., 18, 280 (1979). 6. A. J. Jacobson, in Solid State Chemistry-Compounds, A. K. Cheetham, P. Day, eds., Clarendon Press, Oxford, 1992, p. 182. 7. J. Livage, J. Lamerle, Annu. Rec. Mater. Sci., 12, 103 (1982). 8. R. Schollhorn, F. Klein-Resnick, R. Reinhold, J . Chem. Soc., Chem. Commun., 398 (1979). 9. P. G. Dickens, M. F. Pye, in Intercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982, p. 539. 10. D. W. Murphy, F. J. DiSalvo, J. N. Carides, J. V. Waszczak, Mater. Res. Bull., 13, 1395 (1978).
3.10.3.2.4.2 H,MoO,: Hydrogen-IntercalatedCompounds of Molybdenum Trioxide. In the structure of MOO, the double layers of Moo6octahedra share cis edges along the c axis, while along the a axis they share corners. The octahedra are distorted from the ideal. Individual layers in Moo3 are separated by a true van der Waals gap, and consequently the oxide shows the full range of topotactic redox reactions observed for the transition metal dichalcogenides. The intercalation of M 0 , by hydrogen has been investigated intensively’. H,M03 phases are prepared by techniques described for synthesis of HxV205. Hydrogen insertion occurs with minimal rearrangement of the MOO, structure. In the structure D o . x M o O ~ (Figure 1) the D atoms are attached to bridging 0 atoms as -OD groups in intralayer sites and are not involved in hydrogen bonding between the layers. In contrast, in the structure of D1.68M003 the D atoms are attached to the terminal 0 to form -OD2 groups projecting into the interlayer space. While MOO, is offwhite and insulating, the reduced intercalated phases are opaque blue-black with a metallic sheen having metallic conductivity. The H x M o 0 3 phases are Brclnsted acids. They react with Lewis bases (L) to form intercalation compounds L,H,Mo03
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
202
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.2 H,MoO,: Hydrogen-IntercalatedCompounds of MOO,
Al +xV308(A = Li, Na, Ag, Cu) and Al +x(V308)2(A = Zn, Mg, Ni, Co) structures are formed of (V308), sheets packing A ions’. The structure of V6013can be seen as arising from a (2,3) shear of ReO, (Fig. 3). This shows how the structures of V2O5, VO,(B), and V6013 are derived from ReO, by successive shears. The three-dimensional structure consists of alternating planes of double and single chains of V 0 6 octahedra. Channels made of tricapped cuboctahedra extend through the structure. Treatment of V6013 with n-BuLi yields intercalation compounds LiXV6Ol3with x = 4 at RT and x = 6 at 50’C. The binary transition metal oxides MO, (e.g., M = Mo, Ru, Os, Ir) with the rutile structure form Li,M02 (with x > 1) insertion compounds. When treated with n-BuLi’’, the rutile phase of V 0 2 does not seem to intercalate significant amounts of Li. However, interacalation occurs readily in a metastable form of V 0 2 , designated as V02(B).The structure of VO,(B) can be considered as a (2,2) shear of Re03. It contains one-dimensional channels of tetracapped cuboctahedral cavities. VO,(B) is essentially the V6013structure without the single chains. Li,VO,(B) with x = 0.5 can be prepared. (M. GREENBLATT, B. RAVEAU) 1. P. Hegenmuller, Prog. Solid State Clzeni.,5, 71 (1971). 2. E. Banks, A. Wold, in Preparatioe Inorganic Chemistry, Vol. 4, W. L. Jolly, ed., New York, 1969, p. 252. 3. A. A. Fotiev, B. L. Volkov, B. K. Kapustkin, Vanadium Bronzes, Academy Nauk, Moscow, 1978 (in Russian). 4. See, for example: D. W. Murphy, in Intercalation Chemistry, M. S . Whittingham, A. J. Jacobson, Academic Press, New York, 1982, p. 563. 5. D. W. Murphy, P. A. Christian, F. J. DiSalvo, J. V. Waszczak, Inorg. Chem., 18, 280 (1979). 6. A. J. Jacobson, in Solid State Chemistry-Compounds, A. K. Cheetham, P. Day, eds., Clarendon Press, Oxford, 1992, p. 182. 7. J. Livage, J. Lamerle, Annu. Rec. Mater. Sci., 12, 103 (1982). 8. R. Schollhorn, F. Klein-Resnick, R. Reinhold, J . Chem. Soc., Chem. Commun., 398 (1979). 9. P. G. Dickens, M. F. Pye, in Intercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982, p. 539. 10. D. W. Murphy, F. J. DiSalvo, J. N. Carides, J. V. Waszczak, Mater. Res. Bull., 13, 1395 (1978).
3.10.3.2.4.2 H,MoO,: Hydrogen-IntercalatedCompounds of Molybdenum Trioxide. In the structure of MOO, the double layers of Moo6octahedra share cis edges along the c axis, while along the a axis they share corners. The octahedra are distorted from the ideal. Individual layers in Moo3 are separated by a true van der Waals gap, and consequently the oxide shows the full range of topotactic redox reactions observed for the transition metal dichalcogenides. The intercalation of M 0 , by hydrogen has been investigated intensively’. H,M03 phases are prepared by techniques described for synthesis of HxV205. Hydrogen insertion occurs with minimal rearrangement of the MOO, structure. In the structure D o . x M o O ~ (Figure 1) the D atoms are attached to bridging 0 atoms as -OD groups in intralayer sites and are not involved in hydrogen bonding between the layers. In contrast, in the structure of D1.68M003 the D atoms are attached to the terminal 0 to form -OD2 groups projecting into the interlayer space. While MOO, is offwhite and insulating, the reduced intercalated phases are opaque blue-black with a metallic sheen having metallic conductivity. The H x M o 0 3 phases are Brclnsted acids. They react with Lewis bases (L) to form intercalation compounds L,H,Mo03
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.3 Molybdenum Bronzes A,Mo,O,
203
Figure 1. The D0.36M003structure. [e.g., (pyridine)o.5H~.sMo03]. Cation exchange reactions of H,Mo03 phases and their derivatives in aqueous solution are rapid at RT'. (M. GREENBLATT, 8. RAVEAU) 1. P. G. Dickens, M. F. Pye, in Intercalation Chemistrj, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982, p. 539.
3.1 0.3.2.4.3 Molybdenum Bronzes A,Mo,O,. Electrolyzing fused mixtures of K2Mo0, and M o o 3 yields three unique molybdenum bronzes whose structures and properties differ markedly from the class of cubic sodium tungsten bronzes (see 3.10.3.1.2)'. The molybdenum bronzes form three different stoichiometric compositions and structure types: the blue bronzes, A0.3M003 (A = K, Rb, Tl), which are quasi-onedimensional metals; the red bronzes, A0.33M003 (A = Li, Na, K, Rb, Cs, Tl), which are semiconducting; and the purple bronzes, (A0.9M06017(A = Li, Na, K) and AMo601, (A = Tl), which are quasi-two-dimensional metals. These materials are stoichiometric, or nearly so. These bronzes have been investigated intensively recently, because of their unusual properties, which include quasi-low-dimensional behavior, charge-density-wave (CDW) driven metal-to-insulator transition (MIT), sliding charge-density waves, and insulator-to-superconductor transitions (IST). Several reviews have been published on
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.3 Molybdenum Bronzes A,Mo,O,
203
Figure 1. The D0.36M003structure. [e.g., (pyridine)o.5H~.sMo03]. Cation exchange reactions of H,Mo03 phases and their derivatives in aqueous solution are rapid at RT'. (M. GREENBLATT, 8. RAVEAU) 1. P. G. Dickens, M. F. Pye, in Intercalation Chemistrj, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982, p. 539.
3.1 0.3.2.4.3 Molybdenum Bronzes A,Mo,O,. Electrolyzing fused mixtures of K2Mo0, and M o o 3 yields three unique molybdenum bronzes whose structures and properties differ markedly from the class of cubic sodium tungsten bronzes (see 3.10.3.1.2)'. The molybdenum bronzes form three different stoichiometric compositions and structure types: the blue bronzes, A0.3M003 (A = K, Rb, Tl), which are quasi-onedimensional metals; the red bronzes, A0.33M003 (A = Li, Na, K, Rb, Cs, Tl), which are semiconducting; and the purple bronzes, (A0.9M06017(A = Li, Na, K) and AMo601, (A = Tl), which are quasi-two-dimensional metals. These materials are stoichiometric, or nearly so. These bronzes have been investigated intensively recently, because of their unusual properties, which include quasi-low-dimensional behavior, charge-density-wave (CDW) driven metal-to-insulator transition (MIT), sliding charge-density waves, and insulator-to-superconductor transitions (IST). Several reviews have been published on
204
3.1 0.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.3 Molybdenum Bronzes A,Mo,O,
Figure 1. Schematic structure of the blue bronzes, Ao.3Mo03.
3.1 0.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.3 Molybdenum Bronzes A,Mo,O,
Figure 2. Idealized structure of the red bronzes,
Mclo3.(After Ref. 5.)
Figure 3. Idealized structure of the purple bronzes, A0.9M06017.
205
206
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.3 Molybdenum Bronzes A,Mo,O,
these topic^^-^. These can be also synthesized in polycrystalline and single-crystal form from stoichiometric mixtures of A,Mo04, M o o 3 , and M o o 2 in evacuated quartz tubes heated to 600-650°C by temperature gradient flux growth methods. The blue bronze structure is built of infinite sheets of distorted MOO, octahedra held together by the A cations (Fig. la). The MOO, layers consist of 10 edge- and corner-sharing octahedra linked by corner-sharing along the [OlO] and [1021 directions (Fig. lb). The unique one-dimensional properties, (and the CDW-driven MIT) of the blue bronzes are due to the infinite chains of corner-sharing MOO, octahedra along the b crystallographic direction: most of the 4d electron density is on these Mo sites along the chain. Although the chemical formulas of the red bronzes, A0.33M003(A = Li, K, Rb, Cs, T1) and blue bronzes A0,3Mo03(A = K, Rb, T1) are remarkably similar, their crystal structures are significantly different. In the red bronzes, the unit of structure is six edge/corner-sharing octahedra (vs. 10 in the blue bronzes), which then corner-share along the b-axis and [lo21 direction to form the infinite layers (Fjg. 2). The Mo-0-Mo distances along the b direction are considerably larger ( b 7.7 A) in the red than in the blue bronzes ( b 7.5 A). These differences presumably lead to the 108-109 fold increase in the RT resistivity of the red molybdenum bronze, relative to the blue bronze. The Li
-
-
Figure 4. Schematic structure of Li0.9M06017projected in the ac plane. (After Ref. 6.)
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.4 AXMOPOxides
207
analogue, Li0.33M003,is unique both in its three-dimensional structure and in its physical properties. Because Li' is a small ion, a more tightly packed framework structure can form compared to that of the larger alkali metal ion^^-^. The ideal structure of A 0 . 9 M ~ 6 0 1(A7 = Li, Na, K, TI) is described as slabs of corner-sharing Mo-0 polyhedra. Each slab of Mo-0 polyhedra consists of four layers of Re0,-like MOO, octahedra-sharing corners; these slabs are terminated on each side by a layer of MOO, tetrahedra, which share corners with adjacent M o o 6 octahedra. These are stacked in the c direction and held together by the A cations, which are in 12 0-coordinated icosahedral sites (Fig. 3). The 4d electrons of the molybdenum atoms are located in the two-dimensional slabs, and the physical properties of these materials are highly anisotropic. Again, Li0,9M06017is unique. It forms a network structure with the MOO, and M o o 4 polyhedra interconnected in three dimensions, unlike the other A0.9M06017compounds, where the M o o 4 tetrahedra in adjacent layers do not share corners, so that the Mo-0-Mo bonding, infinite in the a and b directions is disrupted along c (Fig. 4). The structural differences between the Li compound and the other Ao,9M0601 7 phases are manifested in dramatic property differences.Whereas the Na, K, and T1 phases undergo a CDW-driven meta-metal transition, Li0.9M06017exhibits a MIT and it becomes superconducting at 2 KZ4. (M. GREENBLATT, B. RAVEAU) 1. A. Wold, W. Kunnmann, R. J. Arnott, R. J. Ferretti, Inorg. Chem., 3 , 545 (1964). 2. M. Greenblatt, Chem. Rec., 88, 31 (1988). 3. C. Schlenker, ed., Low-Dimensional Electronic Properties of Molybdenum Bronzes and Oxides, Kluwer, Dordrecht, Netherlands, 1989. 4. M. Greenblatt, in Physics and Chemistry of Low-Dimensional Inorganic Conductors, NATO-ASI., C . Schlenker, M. Greenblatt, J. Dumas, S. Van Smaalen, eds., Plenum Press, New York, 1996, p. 15. 5 . N. C. Stephenson, A. D. Wadsley, Acta Crjstallogr., 19, 241 (1965). 6. M. Onoda, K. Toriumi, Y. Matsuda, M. Sato, J . Solid State Chem., 66, 163 (1987).
3.10.3.2.4.4 A,M02 Oxides. The structures of many layered oxides result from association of double Re0,-type chains (DRC). Association of such chains through octahedral corners leads to the formation of two Re03-type layers sharing their edges, which are in fact the (001) crystallographic shear planes encountered in many M n 0 3 n - l oxides, where such layers are held together by van der Waals forces. Association of the DRCs through the edges of octahedra can occur in different ways. Figure 1 shows two ways that yield layered structures observed in several oxide families. When two adjacent DRCs share one edge per unit of four octahedra according to Figure l a (mode I), the structure of brannerite (ThTi,06, Fig. 2) is obtained'. This structure occurs in various oxides including A,V,Mo,-,03 and A,VXW1-,O3 (A = Li, Na, K, Rb, Cs). When two successive layers of DRCs share three edges per unit of four octahedra according to Figure l b (mode 11),the structure formed is characterized by identical layers built up of infinite ribbons of edge-sharing octahedra (Fig. 3a) found in several families of oxides. Three different structural families, which differ from one another only by the relative position of the octahedral layers are known':
(1) The titanates AxTi2-yMy04(A = Rb, TI, Cs; M = Mn, Sc, Al, Mg, Ni, Zn, and Fe), exemplified by Rb,B204 (Fig. 3b); (2) K, (Ti2-gMy)04(M = Mg, Ni, Cu, Fe, Mn, Zn) shown as KxB204(Fig. 3c); and (3) y-FeOOH, lepidocrocite (Fig. 3d), e.g., /I-NaMnO, and LiMnO, (Fig. 3e).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.4 AXMOPOxides
207
analogue, Li0.33M003,is unique both in its three-dimensional structure and in its physical properties. Because Li' is a small ion, a more tightly packed framework structure can form compared to that of the larger alkali metal ion^^-^. The ideal structure of A 0 . 9 M ~ 6 0 1(A7 = Li, Na, K, TI) is described as slabs of corner-sharing Mo-0 polyhedra. Each slab of Mo-0 polyhedra consists of four layers of Re0,-like MOO, octahedra-sharing corners; these slabs are terminated on each side by a layer of MOO, tetrahedra, which share corners with adjacent M o o 6 octahedra. These are stacked in the c direction and held together by the A cations, which are in 12 0-coordinated icosahedral sites (Fig. 3). The 4d electrons of the molybdenum atoms are located in the two-dimensional slabs, and the physical properties of these materials are highly anisotropic. Again, Li0,9M06017is unique. It forms a network structure with the MOO, and M o o 4 polyhedra interconnected in three dimensions, unlike the other A0.9M06017compounds, where the M o o 4 tetrahedra in adjacent layers do not share corners, so that the Mo-0-Mo bonding, infinite in the a and b directions is disrupted along c (Fig. 4). The structural differences between the Li compound and the other Ao,9M0601 7 phases are manifested in dramatic property differences.Whereas the Na, K, and T1 phases undergo a CDW-driven meta-metal transition, Li0.9M06017exhibits a MIT and it becomes superconducting at 2 KZ4. (M. GREENBLATT, B. RAVEAU) 1. A. Wold, W. Kunnmann, R. J. Arnott, R. J. Ferretti, Inorg. Chem., 3 , 545 (1964). 2. M. Greenblatt, Chem. Rec., 88, 31 (1988). 3. C. Schlenker, ed., Low-Dimensional Electronic Properties of Molybdenum Bronzes and Oxides, Kluwer, Dordrecht, Netherlands, 1989. 4. M. Greenblatt, in Physics and Chemistry of Low-Dimensional Inorganic Conductors, NATO-ASI., C . Schlenker, M. Greenblatt, J. Dumas, S. Van Smaalen, eds., Plenum Press, New York, 1996, p. 15. 5 . N. C. Stephenson, A. D. Wadsley, Acta Crjstallogr., 19, 241 (1965). 6. M. Onoda, K. Toriumi, Y. Matsuda, M. Sato, J . Solid State Chem., 66, 163 (1987).
3.10.3.2.4.4 A,M02 Oxides. The structures of many layered oxides result from association of double Re0,-type chains (DRC). Association of such chains through octahedral corners leads to the formation of two Re03-type layers sharing their edges, which are in fact the (001) crystallographic shear planes encountered in many M n 0 3 n - l oxides, where such layers are held together by van der Waals forces. Association of the DRCs through the edges of octahedra can occur in different ways. Figure 1 shows two ways that yield layered structures observed in several oxide families. When two adjacent DRCs share one edge per unit of four octahedra according to Figure l a (mode I), the structure of brannerite (ThTi,06, Fig. 2) is obtained'. This structure occurs in various oxides including A,V,Mo,-,03 and A,VXW1-,O3 (A = Li, Na, K, Rb, Cs). When two successive layers of DRCs share three edges per unit of four octahedra according to Figure l b (mode 11),the structure formed is characterized by identical layers built up of infinite ribbons of edge-sharing octahedra (Fig. 3a) found in several families of oxides. Three different structural families, which differ from one another only by the relative position of the octahedral layers are known':
(1) The titanates AxTi2-yMy04(A = Rb, TI, Cs; M = Mn, Sc, Al, Mg, Ni, Zn, and Fe), exemplified by Rb,B204 (Fig. 3b); (2) K, (Ti2-gMy)04(M = Mg, Ni, Cu, Fe, Mn, Zn) shown as KxB204(Fig. 3c); and (3) y-FeOOH, lepidocrocite (Fig. 3d), e.g., /I-NaMnO, and LiMnO, (Fig. 3e).
208
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.4 A,M02 Oxides
Figure 1. Connecting the double Re03-type chains (DRCs) through their edges: (a) model I and (b) model 11. (After Ref. 3.)
Figure 2. Layered structure of brannerite built up of T i 0 6 edge-sharing octahedra interleaved with Th ions (dots). (After Ref. 1.) The titanates are synthesized by heating mixtures of TiOz, MO, or M z 0 3 and AZCO3. Both structures are composed of identical sheets, which are built up from infinite double ribbons of edge-sharing octahedra between which A ions are inserted. The structures differ only by the relative positions of the octahedral layers. K, (TiZ-yMy)O4 can be deduced from the Rb,(Tiz - y M y ) 0 4 structure by a translation of one layer out of the two by half an octahedral edge along the length of the octahedral ribbon, changing the pseudocubic coordination of A ions (Rb) into prismatic-trigonal coordination (K) (Fig. 3a,b). The lepidocrocrite structure of y-FeOOH (Fig. 3d), can be similarly deduced from that of Rb,(Ti2-,MY)O4 by a simple translation of one layer out of the two by half the height of an octahedron in the direction perpendicular to the plane of the projection.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.4 A,MO, Oxides
..... 0
.
0
209
0 . 0 .
.
Figure 3. A,M20,: (a) infinite layer of octahedra built up from edge-sharing DRCs according to model 11, (b) Rb,M204 structure, (c) K,M204 structure, (d) y-FeOOH lepidocrocite structure, (e) /I-NaMnO, structure forming a close-packed array with sodium (dots) in octahedral coordination, and (f) P-MnO, layers forming octahedral cavities, where Na' or Li' ions can be located. (After Ref. 3.)
210
3.1 0.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.5 Another Family of AXMOBOxides
b-NaMnO, and LiMnO, (Fig. 3c), close-packed structures, are closely related to the three other structures discussed above and can be described as formed from identical layers whose relative position is derived directly from the y-FeOOH by a simple translation of one layer out of the two by half an octahedral edge along the direction parallel to the length of the octahedral ribbons. The b-MnO, forms octahedral cavities, which contain the Na' or Li' ions (Fig. 3f). (M. GREENBLATT, B. RAVEAU)
1. R. Ruh, A. D. Wadsley, Acta Crystollogr., 21, 974 (1966). 2. B. Raveau, Rez. Chim. Miner., 21, 391 (1984). 3. B. Raveau, Rev. Inorg. Chern., 9, 37 (1987).
3.10.3.2.4.5 Another Family of AXMOBOxides (M = V, Cr, Mn, Co, Ni; A = Li, Na). These phases comprise alternating layers of edge-shared M 0 6 octahedra and layers
(c)
Figure 1. Structure of oxides with close-packed ab-type anionic layers: (a) K0,50C002type, (b) K0,,,CoOz-type, and (c) cc-NaMnO,. (After Ref. 2.)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
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3.1 0.3.2 Nonstoichiometric Layer Structure Oxides 3.1 0.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.5 Another Family of AXMOBOxides
b-NaMnO, and LiMnO, (Fig. 3c), close-packed structures, are closely related to the three other structures discussed above and can be described as formed from identical layers whose relative position is derived directly from the y-FeOOH by a simple translation of one layer out of the two by half an octahedral edge along the direction parallel to the length of the octahedral ribbons. The b-MnO, forms octahedral cavities, which contain the Na' or Li' ions (Fig. 3f). (M. GREENBLATT, B. RAVEAU)
1. R. Ruh, A. D. Wadsley, Acta Crystollogr., 21, 974 (1966). 2. B. Raveau, Rez. Chim. Miner., 21, 391 (1984). 3. B. Raveau, Rev. Inorg. Chern., 9, 37 (1987).
3.10.3.2.4.5 Another Family of AXMOBOxides (M = V, Cr, Mn, Co, Ni; A = Li, Na). These phases comprise alternating layers of edge-shared M 0 6 octahedra and layers
(c)
Figure 1. Structure of oxides with close-packed ab-type anionic layers: (a) K0,50C002type, (b) K0,,,CoOz-type, and (c) cc-NaMnO,. (After Ref. 2.)
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercaiaihn Structures 3.10.3.2.4.6 Titanates and Titanoniobates with a Layer Structure
21 1
of alkali metal ions. They are structurally similar to the alkali transition metal dichalcogenides (Fig. 1). Nonstoichiometric phases can be prepared at high temperatures by partial substitution of a tetravalent cation of a different metal, or by partial oxidation of the trivalent M cation. In some cases, metal or 0 vacancies are observed. In general, stable phases cannot be synthesized at high temperature for x < 0.5. The A cations can be deintercalated and reintercalated reversibly by topotactic reactions. Therefore, the layered oxides with A = Li and M = Co and Ni have been investigated intensively for application as cathode materials for secondary Li batteries’. The structures of these oxides, like those of the alkali metal dichalcogenides, depend on the alkali cation content and size and on the ionicity of the M - 0 bond. In the oxides the transition metal is almost always octahedrally coordinated, and pure M O z phases cannot be prepared even at low temperature, because some alkali metal is necessary to stabilize the structure. Staging is not found because the interlayers cannot be emptied completely of the cations.’ (M. GREENBLATT, B. RAVEAU) 1. For a recent review on cathode materials for “rocking chair” lithium batteries, see R. Koksbang, J. Barker, H. Shi, M. Y. Saidi, Solid State lonics, 84, 1 (1996). 2. C. Fouassier, G. Matejka, J. M. Reau, P. Hagenmuller, J . Solid State Chem., 6, 532 (1973); C. Delmas, C. Fouassier, P. Hagenmuller, J . Solid State Chem., 13, 165 (1975).
3.10.3.2.4.6 Titanates and Titanoniobates (or Tantalates) with a Layer Structure: Ion Exchange Properties. Double Re0,-type chains can be linked simultaneously through octahedral corners and edges in the same layer by mode I1 (Fig. 1)’. Titanates, niobates, and tantalates with the general formula AnBZn04”+ correspond to this mode of association of the DRCs. These are known for their ion exchange properties. This large family is related to that of the tunnel structure titanates (3.10.3.3.2). Their structure can also be described as built up of units of 2 x n edge-sharing octahedra, forming infinite ribbons that are n octahedra wide and connected to each other by corner-sharing octahedra. However, the layers are not connected by corner-sharing octahedra as in the tunnel structure titanates, but are held together by cations located in the interlayer space. The oxides N a z T i 3 0 7(Fig. lb), A3Ti5MOI4(A = K, Rb, T1; M = Ta, Nb) (Fig. lc) and CsTi2Nb07 (Fig. 2), correspond to the n = 3 member of the series2. These three structures are characterized by identical layers of [ M 3 0 7 ]x , which result from the association of three DRCs through the edges according to mode 11, and two DRCs through the corners alternately (Fig. la); that is, two edge-sharing mode I1 operations and one corner-sharing operation occur alternately. The oxides N a 2 T i 3 0 7 and A3Ti5MOI4have parallel octahedral ribbons 2 x 3 and can be related to each other by a translation of half the height of an octahedron in the direction perpendicular to the projection. The structure of CsTi’NbO, is somewhat different; two adjacent layers cannot be derived by simple translations-they are related by a glide plane. The relative position of the [M3O7I3;layers changes the coordination and the relative insertion of the A cations. The structure of the n = 4 member, T12Ti409is deduced from that of A3TiSMOl4 (Fig. lc) by replacing the 2 x 3 octahedral units by 2 x 4 edge-sharing octahedral units. TI2Ti4O9is related to the tunnel structure K3Ti8017(see 3.10.3.3.3), which is also built up from 2 x 4 edge-sharing octahedra. The n = 2 member of this series corresponds to ATiMO, (A = K, Rb, T1; M = Nb, Ta) whose [ M 2 0 5 ] sheets are formed from units of 2 x 2 edge-sharing octahedra (Fig. 3)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercaiaihn Structures 3.10.3.2.4.6 Titanates and Titanoniobates with a Layer Structure
21 1
of alkali metal ions. They are structurally similar to the alkali transition metal dichalcogenides (Fig. 1). Nonstoichiometric phases can be prepared at high temperatures by partial substitution of a tetravalent cation of a different metal, or by partial oxidation of the trivalent M cation. In some cases, metal or 0 vacancies are observed. In general, stable phases cannot be synthesized at high temperature for x < 0.5. The A cations can be deintercalated and reintercalated reversibly by topotactic reactions. Therefore, the layered oxides with A = Li and M = Co and Ni have been investigated intensively for application as cathode materials for secondary Li batteries’. The structures of these oxides, like those of the alkali metal dichalcogenides, depend on the alkali cation content and size and on the ionicity of the M - 0 bond. In the oxides the transition metal is almost always octahedrally coordinated, and pure M O z phases cannot be prepared even at low temperature, because some alkali metal is necessary to stabilize the structure. Staging is not found because the interlayers cannot be emptied completely of the cations.’ (M. GREENBLATT, B. RAVEAU) 1. For a recent review on cathode materials for “rocking chair” lithium batteries, see R. Koksbang, J. Barker, H. Shi, M. Y. Saidi, Solid State lonics, 84, 1 (1996). 2. C. Fouassier, G. Matejka, J. M. Reau, P. Hagenmuller, J . Solid State Chem., 6, 532 (1973); C. Delmas, C. Fouassier, P. Hagenmuller, J . Solid State Chem., 13, 165 (1975).
3.10.3.2.4.6 Titanates and Titanoniobates (or Tantalates) with a Layer Structure: Ion Exchange Properties. Double Re0,-type chains can be linked simultaneously through octahedral corners and edges in the same layer by mode I1 (Fig. 1)’. Titanates, niobates, and tantalates with the general formula AnBZn04”+ correspond to this mode of association of the DRCs. These are known for their ion exchange properties. This large family is related to that of the tunnel structure titanates (3.10.3.3.2). Their structure can also be described as built up of units of 2 x n edge-sharing octahedra, forming infinite ribbons that are n octahedra wide and connected to each other by corner-sharing octahedra. However, the layers are not connected by corner-sharing octahedra as in the tunnel structure titanates, but are held together by cations located in the interlayer space. The oxides N a z T i 3 0 7(Fig. lb), A3Ti5MOI4(A = K, Rb, T1; M = Ta, Nb) (Fig. lc) and CsTi2Nb07 (Fig. 2), correspond to the n = 3 member of the series2. These three structures are characterized by identical layers of [ M 3 0 7 ]x , which result from the association of three DRCs through the edges according to mode 11, and two DRCs through the corners alternately (Fig. la); that is, two edge-sharing mode I1 operations and one corner-sharing operation occur alternately. The oxides N a 2 T i 3 0 7 and A3Ti5MOI4have parallel octahedral ribbons 2 x 3 and can be related to each other by a translation of half the height of an octahedron in the direction perpendicular to the projection. The structure of CsTi’NbO, is somewhat different; two adjacent layers cannot be derived by simple translations-they are related by a glide plane. The relative position of the [M3O7I3;layers changes the coordination and the relative insertion of the A cations. The structure of the n = 4 member, T12Ti409is deduced from that of A3TiSMOl4 (Fig. lc) by replacing the 2 x 3 octahedral units by 2 x 4 edge-sharing octahedral units. TI2Ti4O9is related to the tunnel structure K3Ti8017(see 3.10.3.3.3), which is also built up from 2 x 4 edge-sharing octahedra. The n = 2 member of this series corresponds to ATiMO, (A = K, Rb, T1; M = Nb, Ta) whose [ M 2 0 5 ] sheets are formed from units of 2 x 2 edge-sharing octahedra (Fig. 3)
212
3.10.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with Intercalation Structures 3.10.3.2.4.6 Titanates and Titanoniobates with a Layer Structure
Figure 1. Structure of the n = 3 members of the AnB2,04,+z series: (a) association of DRCs through the corners and edges alternately, (b) NazTi307,and (c) A3Ti5NbOI4. (After Ref. 1.)
and result from the combination of one edge-sharing association of the DRCs by mode I1 with one corner-sharing operation3.These oxides are closely related to CsTi2Nb0,. The relative position of the layers and their similarity to the tunnel structure ATi3M09 (see 3.10.3.3.2)enables the empty tunnel structure TizNbZO9to be synthesized from the layer structure HTiNb05. Defect A-cation oxides have also been observed for this (x < 0.15). These structural type corresponding to the composition Al -,.(Til -,MI +,)05 oxides can be easily prepared by heating mixtures of carbonates, AzC03, and oxides, TiOz, MzOs. All these oxides exhibit intercalation and ion exchange properties. Ion exchange can occur in aqueous media, by solid state reaction with chlorides, or in molten salt media; e.g., A2Ti409(A = Li, Na, K, Rb, Cs, Ag) are synthesized from T12Ti409by ion exchange reactions. Similarly, the ion exchange properties of the ATiM05 oxides allow synthesis of
3.1 0.3.2 Nonstoichiometric Layer Structure Oxides 3.10.3.2.4 Oxides with intercalation Structures 3.10.3.2.4.6 Titanates and Titanoniobates with a Layer Structure
213
c
Figure 2. Idealized structure of CsTi2Nb07.(After Ref. 2.)
Figure3. Structure of KTiNb05, the n = 2 member of the AnB2n04n+2 series. (After Ref. 3.)
HTiM05, NH4TiM05, hydrated Li and Na compounds, and the intercalation of alkylammonium ions with long chains. Similar results are observed for AzTiNb07and ATi5MOL4oxides3. Recently Gopalakrishnan reviewed soft chemistry techniques for the
214
3.10 Formation of Non-stoichiometricOxides 3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides
preparation of metastable oxides including those for novel layered titanates and titan~niobates~. (M. GREENBLATT, 8. RAVEAU) 1. 2. 3. 4.
B. Raveau, Rec. Inorg. Chem., 9, 37 (1987). B. Raveau, Rev. Chim Miner., 21, 391 (1984). A. D. Wadsley, Acta Crystallogr., 17, 623 (1964). J. Gopalakrishnan, Muter. Chem., 7, 1265 (1995).
3.10.3.3 Tunnel Structure Oxides'-*
The large oxide family with a tunnel structure is characterized by a wide range of nonstoichiometry. In these compounds, formulated as A,MO,, the host lattice, MO,, which delimits the tunnels, is typically built up from octahedra, or from octahedra and tetrahedra, and sometimes from bipyramids, but rarely from tetrahedra alone. The A ions that are located in the tunnels are generally large (i.e., ionic radius > 1 A), whereas the M elements belong to the first or second transition metal series when they are in octahedral or bipyramidal coordinations but are usually limited to Si, Ge, or P for the tetrahedral coordination. The octahedral structures are most numerous: best known are the bronzes A,Mo03, A,W03, and A,Ti02 (see 3.10.3.1.2),which exhibit semiconducting or metallic properties owing to d electrons in the MO, framework'-*. Several other structures, some related to the previously described framework structures (e.g., rutile), will also be considered, including hollandite and ramsdellite. Among the network compounds formed of octahedra and tetrahedra are phosphates of mixed valent/reduced transition elements, including the Ti9,V9, Mo9.'0, Nb" and W" bronzes and the silicates, and germanates of A6 -xM6(Si/Ge)4026(M = Nb, Ta) and their inter growth^'^. Examples of bipyramidal frameworks are given by P-A,V2O5 vanadium bronzes. Although some tetrahedral oxides are described as tunnel structures (e.g., benitoites14, mi la rite^'^ possible nonstoichiometry in these compounds is limited, and they are not examined here. A large family of intersecting tunnel structures, described for their ion exchange properties, are also not discussed. (M. GREENBLATT, B. RAVEAU)
1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997. 4. A. K. Cheetham, P. Day, eds., Solid State Chemistry Compounds, Clarendon Press, Oxford, 1992. 5. K. J. Rao, ed., Perspectives in Solid State ChemistrT, ed., Narosa Publishing House, New Delhi, 1995. 6. A. D. Wadsley, Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 7. P. Hagenmuller, Prog. Solid State Chem., 5, 71 (1971). 8. B. Raveau, Proc. Indian Nut. Acad., A52, 67 (1986). 9. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 10. G. Costentin, A. Leclaire, M. M. Borel, A. Grandin, P. Labbe, B. Raveau, Rev. Inorg. Chem., 13, 77 (1993). 11. B. Raveau, M. M. Borel, A. Leclaire, A. Grandin, Int. J . Modern Phys., 7, 4109 (1993) 12. M. Greenblatt, Acc. Chem. Res., 29, 219 (1996).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 214
3.10 Formation of Non-stoichiometricOxides 3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides
preparation of metastable oxides including those for novel layered titanates and titan~niobates~. (M. GREENBLATT, 8. RAVEAU) 1. 2. 3. 4.
B. Raveau, Rec. Inorg. Chem., 9, 37 (1987). B. Raveau, Rev. Chim Miner., 21, 391 (1984). A. D. Wadsley, Acta Crystallogr., 17, 623 (1964). J. Gopalakrishnan, Muter. Chem., 7, 1265 (1995).
3.10.3.3 Tunnel Structure Oxides'-*
The large oxide family with a tunnel structure is characterized by a wide range of nonstoichiometry. In these compounds, formulated as A,MO,, the host lattice, MO,, which delimits the tunnels, is typically built up from octahedra, or from octahedra and tetrahedra, and sometimes from bipyramids, but rarely from tetrahedra alone. The A ions that are located in the tunnels are generally large (i.e., ionic radius > 1 A), whereas the M elements belong to the first or second transition metal series when they are in octahedral or bipyramidal coordinations but are usually limited to Si, Ge, or P for the tetrahedral coordination. The octahedral structures are most numerous: best known are the bronzes A,Mo03, A,W03, and A,Ti02 (see 3.10.3.1.2),which exhibit semiconducting or metallic properties owing to d electrons in the MO, framework'-*. Several other structures, some related to the previously described framework structures (e.g., rutile), will also be considered, including hollandite and ramsdellite. Among the network compounds formed of octahedra and tetrahedra are phosphates of mixed valent/reduced transition elements, including the Ti9,V9, Mo9.'0, Nb" and W" bronzes and the silicates, and germanates of A6 -xM6(Si/Ge)4026(M = Nb, Ta) and their inter growth^'^. Examples of bipyramidal frameworks are given by P-A,V2O5 vanadium bronzes. Although some tetrahedral oxides are described as tunnel structures (e.g., benitoites14, mi la rite^'^ possible nonstoichiometry in these compounds is limited, and they are not examined here. A large family of intersecting tunnel structures, described for their ion exchange properties, are also not discussed. (M. GREENBLATT, B. RAVEAU)
1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997. 4. A. K. Cheetham, P. Day, eds., Solid State Chemistry Compounds, Clarendon Press, Oxford, 1992. 5. K. J. Rao, ed., Perspectives in Solid State ChemistrT, ed., Narosa Publishing House, New Delhi, 1995. 6. A. D. Wadsley, Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 7. P. Hagenmuller, Prog. Solid State Chem., 5, 71 (1971). 8. B. Raveau, Proc. Indian Nut. Acad., A52, 67 (1986). 9. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 10. G. Costentin, A. Leclaire, M. M. Borel, A. Grandin, P. Labbe, B. Raveau, Rev. Inorg. Chem., 13, 77 (1993). 11. B. Raveau, M. M. Borel, A. Leclaire, A. Grandin, Int. J . Modern Phys., 7, 4109 (1993) 12. M. Greenblatt, Acc. Chem. Res., 29, 219 (1996).
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
215
13. B. Raveau, Proc. Indian Nat. Acad., 96, 419 (1986). 14. J. Choisnet, A. Deschanvres, B. Raveau, J . Solid State Chem., 4, 209 (1972). 15. N. Nguyen, J. Choisnet, B. Raveau, J . Solid State Chem., 34, 1 (1980).
3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures'-'
In addition to the perovskite bronzes such as Na,WO,, Li,W03, and Ln,W03, which were been described in 3.10.2.3.3, the Magneli tungsten bronzes A,W03 encompass two classes of tunnel structures'. The tetragonal tungsten bronzes (TTB) are formed where A = K; Na: Ba, Pb, and 0.4 < x < 0.60 for K, 0.3 < x < 0.40 for Na, x 0.20 for Ba, and 0.17 < x <: 0.35 for Pb. The hexagonal tungsten bronzes (HTB) A,W03 form with A = K, Rb, Cs, T1, In, Sn, and 0.2 < x 6 0.33. In both structures, the
-
Figure 1. (a) Structure of the tetragonal tungsten bronze (TTB), K,W03: projection onto the (001) plane. (After Ref. 9.) (b) The hexagonal tungsten bronze (HTB)K,,,,WO3: projection onto the (001) plane. (After Ref. 10.)
Figure 2. Projection of the bronzoid Nbl,W,,O,, structure onto the (001) plane. The Nb(W)06 octahedra (hatched squares) form pentagonal tunnels that are partly filled with Nb-0-Nb chains forming N b 0 7 bipyramids (hatched). (After Ref. 15.)
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
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13. B. Raveau, Proc. Indian Nat. Acad., 96, 419 (1986). 14. J. Choisnet, A. Deschanvres, B. Raveau, J . Solid State Chem., 4, 209 (1972). 15. N. Nguyen, J. Choisnet, B. Raveau, J . Solid State Chem., 34, 1 (1980).
3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures'-'
In addition to the perovskite bronzes such as Na,WO,, Li,W03, and Ln,W03, which were been described in 3.10.2.3.3, the Magneli tungsten bronzes A,W03 encompass two classes of tunnel structures'. The tetragonal tungsten bronzes (TTB) are formed where A = K; Na: Ba, Pb, and 0.4 < x < 0.60 for K, 0.3 < x < 0.40 for Na, x 0.20 for Ba, and 0.17 < x <: 0.35 for Pb. The hexagonal tungsten bronzes (HTB) A,W03 form with A = K, Rb, Cs, T1, In, Sn, and 0.2 < x 6 0.33. In both structures, the
-
Figure 1. (a) Structure of the tetragonal tungsten bronze (TTB), K,W03: projection onto the (001) plane. (After Ref. 9.) (b) The hexagonal tungsten bronze (HTB)K,,,,WO3: projection onto the (001) plane. (After Ref. 10.)
Figure 2. Projection of the bronzoid Nbl,W,,O,, structure onto the (001) plane. The Nb(W)06 octahedra (hatched squares) form pentagonal tunnels that are partly filled with Nb-0-Nb chains forming N b 0 7 bipyramids (hatched). (After Ref. 15.)
216
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.1 0.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
W 0 3 host lattice is built up from corner-sharing octahedra forming triangular, square, and pentagonal tunnels in the case of TTB (Fig. la)' and hexagonal tunnels for HTB (Fig. lb)". These compounds are synthesized by reaction of W either with A 2 0 and W 0 3 or
(b)
Figure 3. (a) Structure of Mo10028:view along c. (After Ref. 16.) (b) Structure of th oxide WI8O4': view along b. (After Ref. 17.)
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
217
with tungstates under vacuum. Alkaline earth TTB is synthesized by reaction of alkaline earth halides AX2 (A = Ba, Sr, Ca; X = F, C1) with mixtures of W 0 3 and WOz, taking advantage of the volatility of oxyhalides such as W 0 2 X 2 . The HTB structure can be stabilized for small cations like Li+ and N a t and for divalent ions (A = C a Z + ,SrZt, Ba2+)at high pressure. The presence in both structures of triangular tunnels (Fig. 1) allows the insertion of small cations like Lit and Ta(V), leading to the bronzes A,Li,W03 and the bronzoids (semiconducting, or insulating bronze like phases, with no unpaired d electrons), e.g., K6Ta10.80030.
Figure 4. Structure of M017047: view along c. (After Ref. 18.)
0 7'
n w
Figure 5. Projection of the Tl2W4OI5structure onto the (001)plane. The W atoms (small solid circles) form octahedra that share corners, resulting in HTB slabs interleaved with Tlt cations (open circles). (After Ref. 19.)
218
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
It is noteworthy that the molybdenum bronzes A,Mo03 d o not form isostructural TTB and HTB frameworks when prepared under the same conditions as tungsten bronzes, even though the size and coordination of Mo and W are similar. However, the
(4
(b)
(c)
Figure 6. Association of (a) diamond-shaped ReO,-type slices and (b) HTB slices leading to (c) the ITB structure. (After Ref. 20.)
Figure 7. K2W3OI0:projection of the structure onto (010). (After Ref. 21.)
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
219
tungsten bronzes tend to be three-dimensional as is the case with WO,, while the molybdenum bronzes, like MOO, are two-dimensional. Nevertheless, HTB and TTB A,MoO, bronzes are synthesized at high pressure; e.g., K0.5M003 (TTB) and Rb0.27M003(HTB) are prepared at 1200"C, under 65 kbar by reducing mixtures of molybdates (A2Mo0,) and MOO, by Mo. Tungsten partly can be replaced by other transition metal ions such as Nb(V) and Ta(V), e.g. for HTB A,(M,W1-,)03 (A = K, Rb, T1, Cs; 0.20 < x < 0.33). Niobates and tantalates with an HTB or TTB structure are also synthesized by heating mixtures of
0 Figure 8. (a) Hexagonal A,(V,Mol-,)O,: BaTa206: view along c. (After Ref. 23.)
view along c. (After Ref. 22.) (b) Structure of
220
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.1 0.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes. and Related Structures ~~
M2OS and A C 0 3 or A 2 C 0 3 in air; e.g., HTB K2Ta3.409and TTB K6Ta10.8030, Sr3-xTa301511and niobates such as the well-known "banana", Ba4NazNblo030'2or AM20613(A = Sr, Ba, Pb; M = Nb, Ta), which have been extensively studied for their ferroelectric and nonlinear optical properties are prepared similarly. New analogues of the niobium TTB, Ba6Nblo030,continue to be in~estigated'~. Big cations are not necessary to stabilize these tunnel structures; empty tunnel HTB structures such as MOWl 1 0 3 6 and MoW14O4S have been prepared as whiskers by heating commercial W 0 3 containing Mo as an impurity. Similarly, in the M2Os-WO3 systems (M = Ta, Nb) the TTB structure is stabilized by M-0 chains in the pentagonal tunnels distributed in an ordered manner as in, e.g., NblsW180941s(Fig. 2) and in Ta4W7031which is an ordered intergrowth of the R e 0 3 and TTB structures. The oxides Mo10028,W18049, and M017047 behave similarly and exhibit strongly distorted TTB structures whose pentagonal tunnels are partly occupied by Mo-0 or W-0 chains, respectively (see Fig. 3a). Several tungsten and molybdenum oxides exhibit tunnel structures related to those of HTB and TTB bronzes; e.g., in the edge- and corner-sharing octahedra of the tungsten oxide, w 1 8 0 4 9 forms with empty hexagonal and perovskite tunnels, and with pentagonal tunnels, which are occupied by W-0 chains (Fig. 3b)"j' 17. Similarly, the M017047 oxide is characterized by Mo-0 chains filling pentagonal tunnels, but in this structure another type of tunnel is built up from six corner-sharing octahedra (Fig. 4)13.
Figure 9. Structure of the GTB, Rb3Nb540146:projection onto (001). (After Ref. 24.)
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.1 Tungsten, Molybdenum Bronzes, and Related Structures
22 1
By shearing the HTB structure along the c direction at the level of the apical corners of the WOs octahedra, the HTB slices are shifted with respect to each other, e.g., for T12W4013” (Fig. 5). This structure consists of HTB layers shifted by c/2 alternatively; cohesion between layers is ensured by T1’ ions. The HTB [W03], framework is associated with a diamond-shaped W 0 3 framework leading to formation of structures called intergrowth tungsten bronzes (ITB). These are described as the integrowth of HTB slices with distorted Re03-type slices (Fig. 6). Numerous oxides belong to this family: A,W03 (x < 0.10), ACu3M7OZ1, Ca2T1Nb5015, U M O ~ ~ and O ~U ~M , o 2 0 8 are known’. Although, not so closely related, the K2W3010framework”, which delimits wide tunnels (Fig. 7), can be related to that of HTB tunnels with large tunnels built up from seven octahedra. Octahedral frameworks strongly related to the HTB structure are also known for molybdates and vanadomolybdates21B22.The oxides A,V,Mol -,03(A = K, Rb, Cs; 0 < x < 1.66) and K M o 5 0 1 5 0 H . 2 H 2 0have host lattices consisting of triple rows of and corner-sharing octahedra running along c, just as in HTB (Fig. 8)23. Rb3Nb540146 T1Nb7018are known as Gatehouse tungsten bronzes (GTB)24.These compounds with tetragonal unit cells are the only octahedrally coordinated transition metal, oxides with very large tunnels. The host lattice is related to the HTBs and TTBs; the M3015 and M4O20 octahedral units form the large HTB tunnels where the Rb’ or T1’ ions are located. The pentagonal tunnels are occupied by NbO-, pentagonal bipyramids, and empty perovskite tunnels (Fig. 9). (M. GREENBLATT, 6. RAVEAU) 1. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 2. C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers New York, 1995. 3. C. N. R. Rao, J. Gopalakrishnan, New Directions in Solid State Chemistry, 2nd ed., Cambridge University Press, Cambridge, 1997. 4. A. K. Cheetham, P. Day, eds., Solid State Chemistry Compounds, Clarendon Press, Oxford, 1992. 5. K. J. Rao, ed., Perpectives in Solid State Chemistry, ed., Narosa Publishing House, New Delhi, 1995. 6. A. D. Wadsley, Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 7. P. Hagenmuller, Prog. Solid State Chem., 5, 71 (1971). 8. B. Raveau, Proc. Indian Nut. Acad., A52, 67 (1986). 9. A. Magneli, Acta Chem. Scand., 7, 315 (1953). 10. A. Magneli, Ark. Chem., 1, 213 (1949). 11. T. Siegrist, R. J. Cava, J. J. Krajewski, Muter. Res. Bull., 32, 881 (1997). 12. P. B. Jamieson, J. C. Abrahams, J. L. Bernstein, J . Chem. Phys., 50,4352 (1969). 13. P. Labbe, M. Frey, B. Raveau, J. C. Monier, Acta Crystallogr., Sect. B, 33, 2201 (1977). 14. 0. G. D’yachenko, S. A. Istomin, M. M. Fedotov, E. V. Antipov, G. Svensson, M. Nygren, W. Holm, Muter. Res. Bull., 32, 409 (1997). 15. A. W. Sleight, Acta Chem. Scand., 20, 1102 (1966). 16. A. D. Wadsley, L. Kihlborg, Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 17. A. Magneli, Ark. Chem., I , 223 (1949). 18. L. Kihlborg, Acta Chem. Scand., 14, 1612 (1960). 19. M. Goreaud, P. Labbe, J. C. Monier, B. Raveau, J . Solid State Chem., 30, 311 (1979). 20. L. Kihlborg, R. Sharma, J . Microsc. Spectrosc. Electron., 7, 387 (1982). 21. K. Okada, H. Morikawa, F. Maromo, S. Iwai, Acta Crystollogr., Sect. B, 32, 1522 (1976). 22. J. Galy, M. Darriet, Rea. Chim. Miner., 11, 513 (1974). 23. G. K. Layden, Muter. Res. Bull., 3, 349 (1968). 24. B. M. Gatehouse, M. C. Nesbit, J . Solid State Chem., 33 153 (1980); B. M. Gatehouse, Natl. Bur. Stand. Spec. Publ., 364, 15 (1972); B. M. Gatehouse, J . Less Common Met., 36, 53 (1974).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
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3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.2 Titanium Bronzes and Related Oxides
3.10.3.3.2 Titanium Bronzes and Related Oxides
The bronze Na,Ti02 exhibits tunnels with a square section similar to those observed in the perovskite’. It is prepared by reduction of Na2Ti307in Hz. The [Ti02] host lattice of Na,TiO, is similar to that of the perovskite but differs in that the TiOs octahedra share edges instead of their corners along two directions (Fig. l), while along the third direction, they share corners as in the perovskite. The sodium content incorporated into the tunnels is not well defined (x FZ 0.2), and the tunnels are never fully occupied. The presence of Na’ ions is not necessary to stabilize the [TiOZ], framework; the isotypic A1Nb04 and one form of FeNb04 exhibit the same host lattice characterized by empty tunnels. In Na,Ti02, the Ti is mixed valent, Ti(III)/(IV),and the compound is metallic. A new T i 0 2 form with this structure is prepared from K2Ti8017by ion exchange reactions followed by thermal decomposition’. Chemical or electrochemical insertion of Li, Na, and K into this TiO, form is observed. The Na,TiOz type structure can be limited to slabs connected through single octahedra forming rows of distorted hexagonal tunnels where Na’ ions are located e.g., Na2Ti9019,which is prepared by hydrothermal reactions3. Related to this structure, in that they exhibit similar octahedral units and perovskite tunnels, are those of the oxygen-defect N b 2 0 5 phases M 3 n 0 8 n - 3 ’ that belong to the TiO2-Nb2O5 system and result from a crystallographic shear (see 3.10.3.1.3). The titanates A2Ti6013(A = Na, K, Rb) are the n = 6 member of the A2Tin02n+l homologous series4 with a tunnel structure related to Na,TiO,. The host lattice, [Ti6013], is formed from 2 x 3 edge-sharing octahedra (Fig. 2a); these units are stacked along the b direction creating an infinite octahedral wall that is three octahedra wide (Fig. 2b). In the (010) plane, the units share their corners (Fig. 2c), resulting in rectangular tunnels, called “3P,” linked along two directions through their corners and in the third direction through their edges (Fig. 2b). This network results in rectangular tunnels, corresponding to three face-sharing perovskite tunnels (3P). In these, two perovskite cages out of three are occupied by the A cations (Fig. 2~)’.Such a structure has been observed for Ba2Ti601J,which differs from alkali titanates by the presence of d electrons 3;
Figure 1. Projection of the bronze Na,Ti02 structure onto the (110) plane. The T i 0 6 octahedra (crossed squares) share edges forming square tunnels where the Na’ ions (open circles) are located. (After Ref. 1.)
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.2 Titanium Bronzes and Related Oxides
223
a
Figure 2. Structure of the K2Ti6OI3-typeoxides: (a) structural units of 2 x 3 edge-sharing octahedra, (b) infinite walls of edge-sharing octahedra three octahedra wide, and (c) projection onto (010) showing the rectangular tunnels. (After Ref. 5.)
distributed over the host lattice. Although nonstoichiometry of the A ions can be considered, few are observed. The only phases isolated are the A2- 2xBa3xTi6-x013 (A = Na, K, Rb) compounds, characterized by a double nonstoichiometry on both the 12-fold and octahedral sites.
224
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.2 Titanium Bronzes and Related Oxides
A “4P” structure has been prepared by soft chemistry. The host lattice of this phase, K2Ti8017,is built of 2 x 4 edge-sharing octahedral ( n = 8) units forming “4P” tunnels as illustrated in Figure 3. Recently the Nb analogues K2M2Nb4Ol3 (M = Mg, Fe) of K2Ti8OI7 have been prepared6,’. Similarly, the existence of 2P tunnels corresponding to units of 2 x 2 edge-sharing octahedra ( n = 2) would lead to a hypothetical structure AM409 (Fig. 4a), which has not been observed. Compounds corresponding to this composition [e.g., ATiM309 (A = K, Rb, TI; M = Ta, Nb) and BaTi409] exhibit a chemical twin of this structure (Fig. 4b), which forms pentagonal
Figure 3. Structure of K2Ti8OI7:(a) structural units of 2 x 4 edge-sharing octahedra, (b) projection of the structure showing the rectangular tunnels. (After Ref. 7.)
Figure 4. (a) Structure of the hypothetical compound AM409 with 2 x 2 edge-sharing octahedral units. (b) Structure of ATiM309 (A = K, Rb, TI and M = Ta, Nb) and BaTi409. (After Ref. 8.)
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.3 Hollandite, Psilomelane, Ramsdellite, and Related Oxides
225
tunnels where the A ions are located8.A similar structure with empty pentagonal tunnels is obtained for TizNbz09by decomposition of HTiNb068 in which Li' and N a + are inserted. The similarity of these octahedral units makes their connection possible. This is realized in Na2Ti701S9,which is an ordered intergrowth of the [Ti6013]io and [Ti8Ol7Is host lattices. In the same way, the existence of "2P" tunnels has been demonstrated by synthesis of the compounds (AzTi6013)nA'Ti409(A = Na, K, Rb; A' = Ba, Sr, Pb)", corresponding to the intergrowth of [Ti6013], and hypothetical [Ti409] sI frameworks. Li0.5Ti02,prepared from the anatase polymorph of TiOz by treatment with n-BuLi at RT, has the anatase structure with Li' inserted into the framework cavities. Heating this compound at 500°C transforms it to LiTiz04 with the spinel structure; it is superconducting at 12 K". (M.GREENBLATT, B. RAVEAU)
--
1. A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 2. R. Marchand, L. Brohand, M. Tournoux, Muter. Res. Bull., 15, 1129 (1980). 3. Y. Bando, M. Watanabe, Y. Sekikawa, Acta Crystallogr., Sect. B, 35, 1541 (1979). 4. H. C. Dresdner, M. J. Buerger, Z . Kristallogr., 117, 411 (1962). 5. S. Andersson, A. D. Wadsley, Acta Crystallogr., 15, 194 (1962). 6. N. Kumada, N. Kimura, Muter. Res. Bull., 32, 559 (1997). 7. J. A. Watts, J . Solid State Chem., 1, 319 (1970). 8. A. D. Wadsley, Acta Crystallogr., 17, 623 (1964). 9. A. D. Wadsley, W. G. Mumme, Acta Crystallogr., Sect. B , 24, 392 (1968). 10. M. Hervieu, G. Desgardin, B. Raveau, J . Solid State Chem., 30, 375 (1979). 11. D. W. Murphy, M. Greenblatt, S. M. Zahurak, R. J. Cava, J. V. Waszczak, G. W. Hull, Jr., R. S. Hutton, Rev. Chzm. Miner., 19, 441 (1982). 3.10.3.3.3 Hollandite, Psilomelane, Ramsdellite, and Related Oxides
Based on the M4OZ0units present in the rutile structure, new structures with larger tunnels can be generated. This occurs in the hollandites A,Mn02 and A,Ti02, in bronzes, and in substituted titanates A,(Til -xMx)OZ,with A = K, Rb, T1, Cs, NH4 and M = Mg, Fe, Al, Mn, Sc. The hollandite structure (Fig. 1) is tetragonal and can be derived from the rutile structure by edge-sharing of the octahedra in the M4O20 units'. This network results in large square tunnels that are generally less than half-occupied, x being close to 0.125 in the mineral BaMn,016. The tunnels can be empty, or partially occupied by water molecules, as in x-Mn02. The A,TiOZ hollandites are obtained by H z reduction of the corresponding titanates, for A = K, Rb, Cs; 0.13 < x < 0.25 and for A = Ba, Pb, with much smaller x values ( x < 0.125). This structure can be obtained for smaller cations like sodium (e.g., for NaO,,OMnOz, which is synthesized under O2 pressure)'. Structurally, ramsdellite (./-Mn02) and psilomelane [Ba(HZ0)Mn,O,,] are closely related to rutile and hollandite. The ramsdellite structure is characterized by an orthorhombic cell. The host lattice results from that of the rutile or of hollandite when the M4OZ0unit is replaced by a M 8 0 3 4unit. Such units (Fig. 2a)3 are obtained by replacing each octahedron of the M4OZounit by two edge-sharing octahedra. The [MO,], host lattice of the ramsdellite (Fig. 2b) is obtained by association of the M 8 0 3 4units by their corners along two directions in the (001) plane, and their edges along the c direction forming rectangular tunnels (Fig. 2b). This structure, first observed in :/-MnOz with empty tunnels, is stabilized by small cations such as Li+. Nonstoichiometric ramsdellites,
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.3 Hollandite, Psilomelane, Ramsdellite, and Related Oxides
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tunnels where the A ions are located8.A similar structure with empty pentagonal tunnels is obtained for TizNbz09by decomposition of HTiNb068 in which Li' and N a + are inserted. The similarity of these octahedral units makes their connection possible. This is realized in Na2Ti701S9,which is an ordered intergrowth of the [Ti6013]io and [Ti8Ol7Is host lattices. In the same way, the existence of "2P" tunnels has been demonstrated by synthesis of the compounds (AzTi6013)nA'Ti409(A = Na, K, Rb; A' = Ba, Sr, Pb)", corresponding to the intergrowth of [Ti6013], and hypothetical [Ti409] sI frameworks. Li0.5Ti02,prepared from the anatase polymorph of TiOz by treatment with n-BuLi at RT, has the anatase structure with Li' inserted into the framework cavities. Heating this compound at 500°C transforms it to LiTiz04 with the spinel structure; it is superconducting at 12 K". (M.GREENBLATT, B. RAVEAU)
--
1. A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 2. R. Marchand, L. Brohand, M. Tournoux, Muter. Res. Bull., 15, 1129 (1980). 3. Y. Bando, M. Watanabe, Y. Sekikawa, Acta Crystallogr., Sect. B, 35, 1541 (1979). 4. H. C. Dresdner, M. J. Buerger, Z . Kristallogr., 117, 411 (1962). 5. S. Andersson, A. D. Wadsley, Acta Crystallogr., 15, 194 (1962). 6. N. Kumada, N. Kimura, Muter. Res. Bull., 32, 559 (1997). 7. J. A. Watts, J . Solid State Chem., 1, 319 (1970). 8. A. D. Wadsley, Acta Crystallogr., 17, 623 (1964). 9. A. D. Wadsley, W. G. Mumme, Acta Crystallogr., Sect. B , 24, 392 (1968). 10. M. Hervieu, G. Desgardin, B. Raveau, J . Solid State Chem., 30, 375 (1979). 11. D. W. Murphy, M. Greenblatt, S. M. Zahurak, R. J. Cava, J. V. Waszczak, G. W. Hull, Jr., R. S. Hutton, Rev. Chzm. Miner., 19, 441 (1982). 3.10.3.3.3 Hollandite, Psilomelane, Ramsdellite, and Related Oxides
Based on the M4OZ0units present in the rutile structure, new structures with larger tunnels can be generated. This occurs in the hollandites A,Mn02 and A,Ti02, in bronzes, and in substituted titanates A,(Til -xMx)OZ,with A = K, Rb, T1, Cs, NH4 and M = Mg, Fe, Al, Mn, Sc. The hollandite structure (Fig. 1) is tetragonal and can be derived from the rutile structure by edge-sharing of the octahedra in the M4O20 units'. This network results in large square tunnels that are generally less than half-occupied, x being close to 0.125 in the mineral BaMn,016. The tunnels can be empty, or partially occupied by water molecules, as in x-Mn02. The A,TiOZ hollandites are obtained by H z reduction of the corresponding titanates, for A = K, Rb, Cs; 0.13 < x < 0.25 and for A = Ba, Pb, with much smaller x values ( x < 0.125). This structure can be obtained for smaller cations like sodium (e.g., for NaO,,OMnOz, which is synthesized under O2 pressure)'. Structurally, ramsdellite (./-Mn02) and psilomelane [Ba(HZ0)Mn,O,,] are closely related to rutile and hollandite. The ramsdellite structure is characterized by an orthorhombic cell. The host lattice results from that of the rutile or of hollandite when the M4OZ0unit is replaced by a M 8 0 3 4unit. Such units (Fig. 2a)3 are obtained by replacing each octahedron of the M4OZounit by two edge-sharing octahedra. The [MO,], host lattice of the ramsdellite (Fig. 2b) is obtained by association of the M 8 0 3 4units by their corners along two directions in the (001) plane, and their edges along the c direction forming rectangular tunnels (Fig. 2b). This structure, first observed in :/-MnOz with empty tunnels, is stabilized by small cations such as Li+. Nonstoichiometric ramsdellites,
226
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.3 Hollandite, Psilomelane, Ramsdellite, and Related Oxides
Figure 1. Projection of the hollandite structure A,B02 onto the (001) plane. The BOG octahedra (lozenges) form B4OZ0units that share edges. The result is large square tunnels where the A cations (circles) are located. (After Ref. 1.)
Figure 2. Structure of ramsdellite: (a) B 8 0 3 4units and (b) projection of the structure onto (001). (After Ref. 3.)
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.3 Hollandite, Psilomelane, Ramsdellite, and Related Oxides
227
Figure 3. Projections of the structure of (a) CaFe204 and (b) CaTi204.(After Ref. 8.) where lithium is distributed in the octahedral sites and in the tunnels simultaneously, have been synthesized, including LiFeSnO,, Lil +JLiZx3Fe1 -,Snl+x/3)04 (0 < x < 0.25), and Li3FeSbz08.The lithium ions are tetrahedrally coordinated in the tunnels. The relatively small size of the ramsdellite tunnels does not allow the interpolation of big ions. These tunnels can also be empty, as is the case for y-MnO,, or partially filled with lithium, as in Li2Ti3O7, and one form of LiFeSnO,’. Lithium insertion into these ramsdellite structures has been investigated6,?. Compounds with the psilomelane structure are rare. Besides the barium manganese oxide, generally formulated [Baz-x(H20)x]MnsOlo(1.25 < x < 1.50), the psilomelane structure observed for Nao.40MnOzis the only one that can be obtained without water. The structures of CaFez04 (Fig. 3a) and of CaTi204(Fig. 3b) or NaScTiO, and its isomorphs are closely related to that of ramsdellite. The structures are formed of the same units of two edge-sharing octahedra, also linked by the corners of their octahedra, but in such a way that they from larger tunnels that are similar to pentagonal tunnels, where calcium or sodium ions are located (Fig. 3).’ Numerous oxides form with the CaFeZO4 structure: SrFe204,P-CaCr204,CaV,O,, ASc204(A = Ca, Mg, Sr), SrEuZ04,Aln204 (A = Ca, Sr), CaYb204,NaMM’O, (M = Sc, Fe; M‘ = Ti, Sn, Zr, Hf), BaM204 (M = Ln : Nd-Lu), and S r M 2 0 4(M = Y, La-Ho). These compounds are prepared hydrothermally (e.g., Nao 56Fe0.28Til72O4), or by high pressure methods (e.g., NaAlGeO,). Two other structural types characterized by large, but quite different tunnels can be related to those of the previously described oxides (e.g., Nao ,,Mn02, Na4Mn4Ti50189, and Na3-xRe40910).Both host lattices are built up of units of two and three edgesharing octahedra like hollandite, psilomelane, or ramsdellite, but they differ from these by the presence either of M n 0 5 pyramids or isolated octahedra. Recently, these materials with large tunnel structures have been investigated for applications as possible encapsulates for radioactive wastes and as possible ion exchange materials. (M. GREENBLATT, B. RAVEAU) 1. A. D. Wadsley, in Non-Stoichiometric Compounds, L. Mendelcorn, ed., Academic Press, New York, 1964. 2. J. P. Parant, R. Olazcuaga, M. Devalette, C. Fouassier, P. Hagenmuller, J . Solid State Chem., 3 , l(1971). 3. A. F. Wells, Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1984. 4. B. Morosin, C. Mikkelsen, Acta Crystallogr., Sect. €3, 35, 798 (1979).
228 5. 6. 7. 8. 9. 10.
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice
J. Choisnet, M. Hervieu, B. Raveau, P. Tarte, J. Solid State Chem., 40, (1981). M. Greenblatt, E. Wang, H. Eckert, N. Kimura, R. Herber, Inorg. Chem., 24, 1661 (1985). C. J. Chen, M. Greenblatt, Muter. Res. Bull., 20, 1347 (1985). A. F. Reid, A. D. Wadsley, M. Sienko, Inorg. Chem., 7, 112 (1968). W. G. Mumme, Acta Crystallogr., Sect. B, 24, 1114 (1968). J. Darriet, Acta Crystallogr., Sect. B, 30, 1459 (1974).
3.10.3.3.4 Vanadium Bronzes with a Three-Dimensional Structure
Among the numerous vanadium bronzes, AxV2051-3,only the p phase exhibits a tunnel structure. All others are characterized by layer structures. The preparation is identical to that of the layer bronzes (see 3.10.3.2.4).The V 2 0 5framework is built up from edge- and corner-sharing octahedra and of bipyramids (Fig. l), forming large tunnels where the A ions are located. Saturation of the tunnels would correspond to x = 0.67. A value of x close to the maximum is observed for small cations like lithium (x < 0.62) and copper (x < 0.64), but for larger ions like sodium, silver, cadmium, calcium, lead and potassium, the maximum x value ranges from 0.25 to 0.41 1-3. (M. GREENBLATT, B. RAVEAU)
Figure 1. The structure of p-Li,V205. 1. P. Hagenmuller, Prog. Solid State Chem., 5, 71 (1971). 2 . E. Banks, A. Wold, in Preparatice Inorganic Chemistry, Vol. 4, W. L. Jolly, ed., Wiley, New York, 1988, p. 252. 3. A. A. Fotiev, B. L. Volkov, B. K. Kapustkin, Vanadium Bronzes, Academy Nauk, Moscow, 1978 (in Russian). 3.10.3.3.5 Complex Oxides with Host Lattice Built Up from Octahedra and Tetrahedra
A huge number of compounds with structures built up from octahedra and tetrahedra have been prepared, including the phosphate tungsten', niobium2, molybd e n ~ m ~vanadium, .~, and titanium4 bronzes, and silico and germano niobates and tantalates5. In these, monophosphate Po4 (or silicate, S O 4 or germanate, G e 0 4 ) tetrahedra, or diphosphate, P 2 0 7 (or disilicate, Si207 or digermanate, Ge207) cornersharing tetrahedra replace transition metal M 0 6 octahedra in the Re03-type network structures in an ordered way, thereby creating novel bronzes, or bronzoids with
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
228 5. 6. 7. 8. 9. 10.
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice
J. Choisnet, M. Hervieu, B. Raveau, P. Tarte, J. Solid State Chem., 40, (1981). M. Greenblatt, E. Wang, H. Eckert, N. Kimura, R. Herber, Inorg. Chem., 24, 1661 (1985). C. J. Chen, M. Greenblatt, Muter. Res. Bull., 20, 1347 (1985). A. F. Reid, A. D. Wadsley, M. Sienko, Inorg. Chem., 7, 112 (1968). W. G. Mumme, Acta Crystallogr., Sect. B, 24, 1114 (1968). J. Darriet, Acta Crystallogr., Sect. B, 30, 1459 (1974).
3.10.3.3.4 Vanadium Bronzes with a Three-Dimensional Structure
Among the numerous vanadium bronzes, AxV2051-3,only the p phase exhibits a tunnel structure. All others are characterized by layer structures. The preparation is identical to that of the layer bronzes (see 3.10.3.2.4).The V 2 0 5framework is built up from edge- and corner-sharing octahedra and of bipyramids (Fig. l), forming large tunnels where the A ions are located. Saturation of the tunnels would correspond to x = 0.67. A value of x close to the maximum is observed for small cations like lithium (x < 0.62) and copper (x < 0.64), but for larger ions like sodium, silver, cadmium, calcium, lead and potassium, the maximum x value ranges from 0.25 to 0.41 1-3. (M. GREENBLATT, B. RAVEAU)
Figure 1. The structure of p-Li,V205. 1. P. Hagenmuller, Prog. Solid State Chem., 5, 71 (1971). 2 . E. Banks, A. Wold, in Preparatice Inorganic Chemistry, Vol. 4, W. L. Jolly, ed., Wiley, New York, 1988, p. 252. 3. A. A. Fotiev, B. L. Volkov, B. K. Kapustkin, Vanadium Bronzes, Academy Nauk, Moscow, 1978 (in Russian). 3.10.3.3.5 Complex Oxides with Host Lattice Built Up from Octahedra and Tetrahedra
A huge number of compounds with structures built up from octahedra and tetrahedra have been prepared, including the phosphate tungsten', niobium2, molybd e n ~ m ~vanadium, .~, and titanium4 bronzes, and silico and germano niobates and tantalates5. In these, monophosphate Po4 (or silicate, S O 4 or germanate, G e 0 4 ) tetrahedra, or diphosphate, P 2 0 7 (or disilicate, Si207 or digermanate, Ge207) cornersharing tetrahedra replace transition metal M 0 6 octahedra in the Re03-type network structures in an ordered way, thereby creating novel bronzes, or bronzoids with
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
228 5. 6. 7. 8. 9. 10.
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice
J. Choisnet, M. Hervieu, B. Raveau, P. Tarte, J. Solid State Chem., 40, (1981). M. Greenblatt, E. Wang, H. Eckert, N. Kimura, R. Herber, Inorg. Chem., 24, 1661 (1985). C. J. Chen, M. Greenblatt, Muter. Res. Bull., 20, 1347 (1985). A. F. Reid, A. D. Wadsley, M. Sienko, Inorg. Chem., 7, 112 (1968). W. G. Mumme, Acta Crystallogr., Sect. B, 24, 1114 (1968). J. Darriet, Acta Crystallogr., Sect. B, 30, 1459 (1974).
3.10.3.3.4 Vanadium Bronzes with a Three-Dimensional Structure
Among the numerous vanadium bronzes, AxV2051-3,only the p phase exhibits a tunnel structure. All others are characterized by layer structures. The preparation is identical to that of the layer bronzes (see 3.10.3.2.4).The V 2 0 5framework is built up from edge- and corner-sharing octahedra and of bipyramids (Fig. l), forming large tunnels where the A ions are located. Saturation of the tunnels would correspond to x = 0.67. A value of x close to the maximum is observed for small cations like lithium (x < 0.62) and copper (x < 0.64), but for larger ions like sodium, silver, cadmium, calcium, lead and potassium, the maximum x value ranges from 0.25 to 0.41 1-3. (M. GREENBLATT, B. RAVEAU)
Figure 1. The structure of p-Li,V205. 1. P. Hagenmuller, Prog. Solid State Chem., 5, 71 (1971). 2 . E. Banks, A. Wold, in Preparatice Inorganic Chemistry, Vol. 4, W. L. Jolly, ed., Wiley, New York, 1988, p. 252. 3. A. A. Fotiev, B. L. Volkov, B. K. Kapustkin, Vanadium Bronzes, Academy Nauk, Moscow, 1978 (in Russian). 3.10.3.3.5 Complex Oxides with Host Lattice Built Up from Octahedra and Tetrahedra
A huge number of compounds with structures built up from octahedra and tetrahedra have been prepared, including the phosphate tungsten', niobium2, molybd e n ~ m ~vanadium, .~, and titanium4 bronzes, and silico and germano niobates and tantalates5. In these, monophosphate Po4 (or silicate, S O 4 or germanate, G e 0 4 ) tetrahedra, or diphosphate, P 2 0 7 (or disilicate, Si207 or digermanate, Ge207) cornersharing tetrahedra replace transition metal M 0 6 octahedra in the Re03-type network structures in an ordered way, thereby creating novel bronzes, or bronzoids with
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.1 Phosphate Tungsten Bronzes (PTB)
229
low-dimensional properties. The structural and physical properties of these interesting compounds have been reviewed in several recent reports'-5.
(M.GREENBLATT, B. RAVEAU) 1. For recent reviews: M. Greenblatt, Acc. Chem. Res., 29,219 (1996); M. Greenblatt, Int. J . Modern Phvs. B, 7, 3937 (1993). 2. For a review: B. Raveau, M. M. Borel, A. Leclaire, A. Grandin, Int. J . Modern Phys. B, 7, 4109 (1993). 3. G. Costentin, A. Leclaire, M. M. Borel, A. Grandin, B. Raveau, Rev. Inorg. Chem., 1 3 , 77 (1993). 4. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 5 . C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995.
3.10.3.3.5.1 Phosphate Tungsten Bronzes (PTB). The PTBs are reduced ternary and quarternary transition metal phosphate compounds, A,P,W,O,, where some of the W 0 6 octahedra in the Re0,-type slabs are replaced in an ordered fashion by either monophosphate, PO4, or diphosphate, P z 0 7groups. These show bronzelike properties, including intense color, metallic sheen, high electronic conductivity, and metal-to-insulator transitions driven by charge-density-wave instabilities'. Three major structural classes of phosphate tungsten bronzes are known: (1) the monophosphate tungsten bronzes with pentagonal tunnels (MPTB,) with the general (2) the monophosphate bronzes with hexagonal tunnels formula (P02)4(W03)zm2; (MPTB,,) with general formula A,(P0z)4(W03)zmwith A = Na or K3; and (3) the diphosphate tungsten bronzes (DPTB) with general formula Ax(P204)2(W03)zm, where
a
T (4 Figure 1. Schematic structure of the monophosphate tungsten bronzes (MPTB,), (P0z)4(W03)z,,,:(a) m = 2; (b) m = 4, 6, 8; (c) m = 5, 7 , 9.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.1 Phosphate Tungsten Bronzes (PTB)
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low-dimensional properties. The structural and physical properties of these interesting compounds have been reviewed in several recent reports'-5.
(M.GREENBLATT, B. RAVEAU) 1. For recent reviews: M. Greenblatt, Acc. Chem. Res., 29,219 (1996); M. Greenblatt, Int. J . Modern Phvs. B, 7, 3937 (1993). 2. For a review: B. Raveau, M. M. Borel, A. Leclaire, A. Grandin, Int. J . Modern Phys. B, 7, 4109 (1993). 3. G. Costentin, A. Leclaire, M. M. Borel, A. Grandin, B. Raveau, Rev. Inorg. Chem., 1 3 , 77 (1993). 4. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 5 . C. N. R. Rao, B. Raveau, Transition Metal Oxides, VCH Publishers, New York, 1995.
3.10.3.3.5.1 Phosphate Tungsten Bronzes (PTB). The PTBs are reduced ternary and quarternary transition metal phosphate compounds, A,P,W,O,, where some of the W 0 6 octahedra in the Re0,-type slabs are replaced in an ordered fashion by either monophosphate, PO4, or diphosphate, P z 0 7groups. These show bronzelike properties, including intense color, metallic sheen, high electronic conductivity, and metal-to-insulator transitions driven by charge-density-wave instabilities'. Three major structural classes of phosphate tungsten bronzes are known: (1) the monophosphate tungsten bronzes with pentagonal tunnels (MPTB,) with the general (2) the monophosphate bronzes with hexagonal tunnels formula (P02)4(W03)zm2; (MPTB,,) with general formula A,(P0z)4(W03)zmwith A = Na or K3; and (3) the diphosphate tungsten bronzes (DPTB) with general formula Ax(P204)2(W03)zm, where
a
T (4 Figure 1. Schematic structure of the monophosphate tungsten bronzes (MPTB,), (P0z)4(W03)z,,,:(a) m = 2; (b) m = 4, 6, 8; (c) m = 5, 7 , 9.
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.10.3.3.5.1 Phosphate Tungsten Bronzes (PTB)
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m=4
m=5
m=8
m=7
m=9
(c) Figure 1. (Continued)
A = K, Rb, T1, Ba4. Recently, the structural and physical properties of all PTBs were reviewed'. The homologous series of general formula (P0,),(W03)2m,where m is an integer (2,4-16) represents the family MPTB,'. In addition, Ax(P02)4(W03)2m with A = Na, K; x < 1 also forms with this structure. The structure of these is described by the stacking, along the orthorhombic [OOl] direction, of Re03-type slabs of corner-sharing W 0 6 octahedra. The slabs are connected by corner-sharing with PO4 tetrahedra, forming layers in the ab plane of the orthorhombic unit cell (Fig. 1).The strings of octahedra from
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.10.3.3.5.1 Phosphate Tungsten Bronzes (PTB)
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~~
one slab to the next are related by 180" and run in zigzag fashion. At the juncture between two Re03-type slabs, corner-sharing octahedra and tetrahedra form pentagonal tunnels, which are empty in the (P02)4(W03)2m phases, but may be occupied partially by the smaller alkali metal ions in Ax(P02)4(W03)2m [Na, K, (Na, Li), (K, Na); x < lI5.The value of m determines the width of the Re03-type of slabs. For even-m-members the number of W 0 6 octahedra in the slabs is mi2 (Fig. la, m = 2; Fig. lb, m = 4,6, 8), while for odd-m members there are (m + 1)/2 and (m - 1)/2 strings of octahedra alternating in adjacent Re03-type of slabs that repeat in a zigzag fashion (Fig. lc, m = 5,7,9). The a and b lattice parameters are almost independent of m (a z 5.3 and b E 6.6 A), while c varies according to the empirical formula c (4.9 3.1 x m) A'. The m = 6 member of the MPTB, is isostructural with y-Mo4OI1, with PO4 replacing the M o o 4 tetrahedra and of course, W 0 6 octahedra replacing the M o o 6 octahedra2. The m = 4,6, and 7 phases of MPTBs are metallic at RT and partly because of the quasi-low-dimensional structure, electronic correlations lead to CDW-driven MITs that are investigated inten~ively.',~~~ In addition to the empty pentagonal tunnels, there are empty cuboctahedral cavities in the Re03 slabs of the MPTBs. This structural feature and the mixed valency of W (Wv'/W") suggested that lithium and/or sodium ions might be electrochemically and reversibly inserted into these phases for possible applications as cathode materials in secondary batteries and related electrochemical devices. Reactions of MPTB with nbutyllithium and sodium naphthalide, respectively, indicate that indeed, two Lit and 1 N a + ions per W may insert into various MPTBs8. The monophosphate tungsten bronzes with hexagonal tunnels (MPTB,), Ax(P02)4(W03)2m form with A = Na, K; the value of x depends on A and m and ranges
+
-
a
I
Figure 2. Schematic structure of the monophosphate tungsten bronzes A,(P02)4 (W03)2mwith hexagonal tunnels MPTBh (m = 6).
232
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.1 Phosphate Tungsten Bronzes (PTB)
Figure 3. Schematic structure of the diphosphate tungsten bronzes (DPTB) Ax(P20& (WO,),, with m = 8.
between 1.75 and 3; compounds with m from 4 to 13 have been The structures of MPTBhs are closely related to those of MPTB,s. Corner-sharing WOs slabs of ReO, type are connected through PO4 planes. At the juncture between two octahedral layers, the octahedra and tetrahedra corner-share to form hexagonal tunnels (Fig. 1) where the A cations are located. The structure of the m = 4 member of Ax(P02)4(W03)2m is similar to that of vpMo4OI1 with PO4 replacing the M o o 4 tetrahedra at the edges of the Re03-like blocks”. The structures of MPTBhs differ from those of MPTB,s by the relative orientation of the layers. In MPTBhs the octahedra strings exhibit a zigzag configuration (Fig. 1) while in MPTB,s, the strings of octahedra remain parallel from one Re03-type layer to the next (Fig. 2). The host lattice of the diphosphate tungsten bronzes (DPTB) with general formula (A = K, Rb, T1, Ba)4 is built up from Re03-type slabs of cornerA,(P204)2(W03)2m sharing WOd octahedra connected through PzO, groups and thus separated by rows of distorted hexagonal tunnels where the A’ ions are located (Fig. 3). Typically the compounds are synthesized in polycrystalline form by a two-step process. A mixture of (NH4)2HP04and W 0 3 (and alkali carbonate in the A-P-W-0 compositions) is heated at -650°C to decompose the phosphate (carbonate). The product of this reaction is mixed with the appropriate amount of W and heated in ar evacuated quartz tube for prolonged periods at > 1000”C2.3.This synthesis often yield small single crystals, which are large enough for single-crystal X-ray structure analysis
3.1 0.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.10.3.3.5.2 Phosphate Niobium Bronzes (PNB)
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but too small for physical measurements. Large single crystals of these phases have been grown by chemical vapor transport or flux techniques'. (M. GREENBLATT, B. RAVEAU)
1. For recent reviews: M. Greenblatt, Ace. Chem. Res., 29,219 (1996); M. Greenblatt., Int J . Modern Phys. B, 7, 3937 (1993). 2. J. P. Giroult, M. Goreaud, P. Labbe, B. Raveau, Acta Crystallogr. Sect. B, 37, 2139 (1981); A. Benmoussa, P. Labbe, D. Groult, B. Raveau, J . Solid State Chem., 44, 318 (1982); P. Labbe, M. Goreaud, B. Raveau, J . Solid State Chem., 61,324 (1986); S. L. Wang, C. C. Wang, K. H. Lii, J . Solid State Chem., 82,298 (1989); B. Domenges, M. Hervieu, R. J. D. Tilley, B. Raveau, J . Solid State Chem., 54, 10 (1984); B. Domenges, F. Studer, B. Raveau, Muter. Res. Bull., 18, 669 (1983). 3. M. Lamire, P. Labbe, M. Goroud, B. Raveau, J . Solid State Chem., 66, 64 (1987). 4. M. Lamire, P. Labbe, M. Goreaud, B. Raveau, J . Solid State Chem., 71, 342 (1987). 5. E. Wang, M. Greenblatt, J . Solid State Chem., 68, 38 (1987). 6. E. Canadell, M.-H. Whangbo, Int. J . Modern Phys. B, 7, 4005 (1993). 7. P. Foury, J. P. Pouget, Int. J . Modern Phys., B7, 3973 (1993). 8. E. Wang, M. Greenblatt, J . Solid State Chem., 68, 38 (1987). 9. B. Raveau, Proc. Indian Nut. Sci. Acad., A52, 67 (1986); M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J. Solid State Inorg. Chem., 28, 93 (1991). 10. L. Kihlborg, Ark. Kem., 21, 365 (1963).
3.1 0.3.3.5.2 Phosphate Niobium Bronzes (PNB). Several niobium phosphate bronzes with a tunnel structure have been discovered'. The monophosphate niobium bronzes Na,(P02)4(Nb03)2, are isostructural with the MPTB,s. The phases Na2+xNb6P4026(0 < x < 0.75) (Fig. la)2and Na3BaNb8P4032(Fig. lb)3,representing the m = 3 and 4 members, respectively, are prepared from stoichiometric mixtures of the appropriate constituent oxides in evacuated quartz tubes by solid state reactions at high temperature. Structurally they are similar to the corresponding MPTBs, except that in the latter the m = 3 phase is different. Single crystals of Na2.63Nb6P4026 show anisotropic conductivity like the PTBs, but the niobium bronzes are semiconducting4. Intergrowth of the m = 3 and m = 4 phases in Na,-,Nb,P402, has been observed5. A monophosphate niobium bronze Na4Nb~P6035,which is related to the diphosphate tungsten bronzes with pentagonal tunnels, has also been characterized6. The phosphate tungsten bronze KNb3P3015,with an orthorhombic structure, has a host lattice formed of N b 0 6 octahedra and single PO4 tetrahedra sharing corners. In the (001) plane the N b 0 6 octahedra share corners, forming zigzag chains running along the b axis (Fig. 2a), whereas along c, there are infinite [PNbO'] cc chains with N b 0 6 and PO4 polyhedra alternating (Fig. 2b). It is clear from Figure 2a, that the double chain of NbO, octahedra, bordered with PO4 tetrahedra (the latter replacing an N b 0 6 octahedron) has exactly the same arrangement as the TTB structure. There are [Nb3P3021]r ribbons in which the characteristic pentagonal, square and triangular cavities of the TTB structure can be recognized'. The pentagonal tunnels are larger than in the TTBs and are partially occupied by K + ions. The phases K7Nb14+xP9-x060 and K3Nb6P4026,represent the n = 2 and n = so members of the orthorhombic family PNB, (K3Nb6P4026),KNb2P08. The idealized structure of the Nb14P9060framework viewed along the c direction in Figure 3a shows three unique polyhedral chains: [PNb4014]3c (labeled a), and running along the a axis, and [Nb03] (labeled b l ) and [PNb,O,] 3c (labeled b2) running along the b axis. The projection of the structure along [loo] in Figure 3b shows [PNb4OI4] 3c chains running along the c direction, like those observed in several Mo and W phosphates'. The most ~
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
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but too small for physical measurements. Large single crystals of these phases have been grown by chemical vapor transport or flux techniques'. (M. GREENBLATT, B. RAVEAU)
1. For recent reviews: M. Greenblatt, Ace. Chem. Res., 29,219 (1996); M. Greenblatt., Int J . Modern Phys. B, 7, 3937 (1993). 2. J. P. Giroult, M. Goreaud, P. Labbe, B. Raveau, Acta Crystallogr. Sect. B, 37, 2139 (1981); A. Benmoussa, P. Labbe, D. Groult, B. Raveau, J . Solid State Chem., 44, 318 (1982); P. Labbe, M. Goreaud, B. Raveau, J . Solid State Chem., 61,324 (1986); S. L. Wang, C. C. Wang, K. H. Lii, J . Solid State Chem., 82,298 (1989); B. Domenges, M. Hervieu, R. J. D. Tilley, B. Raveau, J . Solid State Chem., 54, 10 (1984); B. Domenges, F. Studer, B. Raveau, Muter. Res. Bull., 18, 669 (1983). 3. M. Lamire, P. Labbe, M. Goroud, B. Raveau, J . Solid State Chem., 66, 64 (1987). 4. M. Lamire, P. Labbe, M. Goreaud, B. Raveau, J . Solid State Chem., 71, 342 (1987). 5. E. Wang, M. Greenblatt, J . Solid State Chem., 68, 38 (1987). 6. E. Canadell, M.-H. Whangbo, Int. J . Modern Phys. B, 7, 4005 (1993). 7. P. Foury, J. P. Pouget, Int. J . Modern Phys., B7, 3973 (1993). 8. E. Wang, M. Greenblatt, J . Solid State Chem., 68, 38 (1987). 9. B. Raveau, Proc. Indian Nut. Sci. Acad., A52, 67 (1986); M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J. Solid State Inorg. Chem., 28, 93 (1991). 10. L. Kihlborg, Ark. Kem., 21, 365 (1963).
3.1 0.3.3.5.2 Phosphate Niobium Bronzes (PNB). Several niobium phosphate bronzes with a tunnel structure have been discovered'. The monophosphate niobium bronzes Na,(P02)4(Nb03)2, are isostructural with the MPTB,s. The phases Na2+xNb6P4026(0 < x < 0.75) (Fig. la)2and Na3BaNb8P4032(Fig. lb)3,representing the m = 3 and 4 members, respectively, are prepared from stoichiometric mixtures of the appropriate constituent oxides in evacuated quartz tubes by solid state reactions at high temperature. Structurally they are similar to the corresponding MPTBs, except that in the latter the m = 3 phase is different. Single crystals of Na2.63Nb6P4026 show anisotropic conductivity like the PTBs, but the niobium bronzes are semiconducting4. Intergrowth of the m = 3 and m = 4 phases in Na,-,Nb,P402, has been observed5. A monophosphate niobium bronze Na4Nb~P6035,which is related to the diphosphate tungsten bronzes with pentagonal tunnels, has also been characterized6. The phosphate tungsten bronze KNb3P3015,with an orthorhombic structure, has a host lattice formed of N b 0 6 octahedra and single PO4 tetrahedra sharing corners. In the (001) plane the N b 0 6 octahedra share corners, forming zigzag chains running along the b axis (Fig. 2a), whereas along c, there are infinite [PNbO'] cc chains with N b 0 6 and PO4 polyhedra alternating (Fig. 2b). It is clear from Figure 2a, that the double chain of NbO, octahedra, bordered with PO4 tetrahedra (the latter replacing an N b 0 6 octahedron) has exactly the same arrangement as the TTB structure. There are [Nb3P3021]r ribbons in which the characteristic pentagonal, square and triangular cavities of the TTB structure can be recognized'. The pentagonal tunnels are larger than in the TTBs and are partially occupied by K + ions. The phases K7Nb14+xP9-x060 and K3Nb6P4026,represent the n = 2 and n = so members of the orthorhombic family PNB, (K3Nb6P4026),KNb2P08. The idealized structure of the Nb14P9060framework viewed along the c direction in Figure 3a shows three unique polyhedral chains: [PNb4014]3c (labeled a), and running along the a axis, and [Nb03] (labeled b l ) and [PNb,O,] 3c (labeled b2) running along the b axis. The projection of the structure along [loo] in Figure 3b shows [PNb4OI4] 3c chains running along the c direction, like those observed in several Mo and W phosphates'. The most ~
234
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.2 Phosphate Niobium Bronzes (PNB)
Figure 1. (a) Projection of the Na2+xNb6P4026structure onto the (001) plane. (b) Projection of the Na3BaNb,P,032 structure onto the (010) plane. (After Ref. 1.)
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.10.3.3.5.2 Phosphate Niobium Bronzes (PNB)
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Figure 2. Projection of KNb3P3015structure (a) along c showing the monophosphate PO, groups and the pentagonal tunnels and (b) along the a direction, showing the [PNbO,] ic chains. (After Ref. 7 . ) striking feature of this latter view is its similarity to the ITB structure. The Nb14P9060 framework is formed by stacking along a of [P2Nb3OI3lr layers derived from the [Mo5015]3c host lattice of S b 2 M 0 , 0 0 3 ,(Fig. 2c) by repIacing two octahedra out offive
236
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.2Phosphate Niobium Bronzes (PNB)
Figure 3. The K7Nb14P9060structure. (a) Idealized framework Nb14P9060along the c axis, showing the perovskitic tunnels (PT1) and chains of [PNb4014] (labeled a), [Nb03]= (labeled b l ) and [PNb,O,], (labeled b2) running along the b axis. (b) Projection of K7Nb14P9060onto the (100) plane. (c) The ITB structure of Sb2M010031. (d) Projection of the structure of K7Nb14P9060along the b axis showing the brownmillerite (BMT), HTB (HTB2), and perovskite tunnels (PT2). (After Ref. 1.)
3.10.3.3 Tunnel Structure Oxides 3.10.3.3.5 Complex Oxides with Host Lattice 3.10.3.3.5.3 Phosphate Molybdenum Oxides
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by PO4 tetrahedra'. There are two types of hexagonal rings in the [P2Nb3OI3] layers: one is similar to those seen in HTBs and the other similar to those observed in the brownmillerite-type structures (e.g., Ca2Fez05). The similarity between the K7Nb14txP9-x060and Sb2M010031of the ITB series is clear in Figure 3b and c. The K f ions are in several of the intersecting tunnels, as illustrated in Figure 3d. The PNB K6.1Ba0.63Nb14P9060,isostructural with K7Nb14+.P9-xo60, shows anisotropic transA large family of monophosphate port properties and semiconducting behavior niobium bronzes isostructural with Cao.stxCs,Nb,024, whose structure is related to the HTBs, have been prepared with various divalent monovalent cations substituted for the Ca and Cs sites, respectively".
'.
(M. GREENBLATT, B. RAVEAU)
1. B. Raveau, M. M. Borel, A. Leclaire, A. Grandin, Int. J . Modern Phys. B, 7, 4109 (1993). 2. B. Benabbas, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, J . Solid State Chem., 95, 245 (1991). 3. G. Costentin, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, Mater. Res. Bull., 26,1051 (1991). 4. J. Xu, M. Greenblatt, J . Solid State Chem., 121, 273 (1996). 5. B. Benabbas, H. Leligny, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, J . Solid State Chem., 101, 137 (1992). 6. B. Benabbas, M. M. B o d , A. Grandin, A. Leclaire, B. Raveau, J . Solid State Chem., 89, 75 (1990). 7. A. Leclaire, M. M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 80, 12 (1989). 8. A. Leclaire, B. Benabbas, M. M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 83, 245 (1989). 9. P. M. Parmentier, C. Gleitzer, A. Courtois, J. Protas, Acta Crystallogr., Sect. B , 35, 1963 (1979). 10. J. Xu, T. Emge, K. V. Ramanujachary, M. Greenblatt, J . Solid State Chern., 125, 192 (1996). 11. G. Costentin, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, Mater. Res. Bull., 26, 301 (1991).
3.10.3.3.5.3 Phosphate Molybdenum Oxides. Molybdenum almost certainly is expected to from phosphate bronzes like those found for W, with an average valence between 5 and 6. Indeed, the framework of the MPTB, with m = 6 is very similar to that of pMo4OI1,which contains Re0,-like slabs of MOO, octahedra connected by bridging MOO, tetrahedra. To date no analogous phosphate molybdenum bronzes have been found. Rather, a variety of insulating phosphate molybdenum oxides are known in which molybdenum displays well-defined valences of 5, 4 and even the very unusual 3. Mixed valence compounds are also seen, but they are quite different in structure from the PTBs. A few examples will illustrate these differences. (Reduced phosphate molybdenum oxides are reviewed in detail by Borel'.) Na,MoP,07 is an example of mixed valency in these systems where a range of non-stoichiometry also exists. A projection of the structure is shown in Figure 1. The building blocks are MOO, octahedra and P z 0 7 groups. The MOO, octahedra share corners with P,07 and are thus isolated in the structure, localizing all d electrons. In the process distorted octagonal and hexagonal tunnels form with the Na' ions residing in the octagonal tunnels off-center near the walls in sites that are partially occupied in a disordered fashion. In a stoichiometric trivalent NaMoP,O, phase with the NaFeP207 structure' layers of P207 groups connect isolated MOO, octahedra. Distorted octagonal cavities form in the Mo-0-P network where the Na' ions reside. Two different sites exist for Mo, one of which has Mo-0 bond distances much longer than might be expected for Mo(III), suggesting that it might be possible to detect the compound with respect to N a f and create a mixed valence compound. Small clusters of edge- and corner-sharing MOO, octahedra are found in several cesium molybdenum phosphates. These groups are separated from each other by
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
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by PO4 tetrahedra'. There are two types of hexagonal rings in the [P2Nb3OI3] layers: one is similar to those seen in HTBs and the other similar to those observed in the brownmillerite-type structures (e.g., Ca2Fez05). The similarity between the K7Nb14txP9-x060and Sb2M010031of the ITB series is clear in Figure 3b and c. The K f ions are in several of the intersecting tunnels, as illustrated in Figure 3d. The PNB K6.1Ba0.63Nb14P9060,isostructural with K7Nb14+.P9-xo60, shows anisotropic transA large family of monophosphate port properties and semiconducting behavior niobium bronzes isostructural with Cao.stxCs,Nb,024, whose structure is related to the HTBs, have been prepared with various divalent monovalent cations substituted for the Ca and Cs sites, respectively".
'.
(M. GREENBLATT, B. RAVEAU)
1. B. Raveau, M. M. Borel, A. Leclaire, A. Grandin, Int. J . Modern Phys. B, 7, 4109 (1993). 2. B. Benabbas, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, J . Solid State Chem., 95, 245 (1991). 3. G. Costentin, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, Mater. Res. Bull., 26,1051 (1991). 4. J. Xu, M. Greenblatt, J . Solid State Chem., 121, 273 (1996). 5. B. Benabbas, H. Leligny, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, J . Solid State Chem., 101, 137 (1992). 6. B. Benabbas, M. M. B o d , A. Grandin, A. Leclaire, B. Raveau, J . Solid State Chem., 89, 75 (1990). 7. A. Leclaire, M. M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 80, 12 (1989). 8. A. Leclaire, B. Benabbas, M. M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 83, 245 (1989). 9. P. M. Parmentier, C. Gleitzer, A. Courtois, J. Protas, Acta Crystallogr., Sect. B , 35, 1963 (1979). 10. J. Xu, T. Emge, K. V. Ramanujachary, M. Greenblatt, J . Solid State Chern., 125, 192 (1996). 11. G. Costentin, M. M. Borel, A. Grandin, A. Leclaire, B. Raveau, Mater. Res. Bull., 26, 301 (1991).
3.10.3.3.5.3 Phosphate Molybdenum Oxides. Molybdenum almost certainly is expected to from phosphate bronzes like those found for W, with an average valence between 5 and 6. Indeed, the framework of the MPTB, with m = 6 is very similar to that of pMo4OI1,which contains Re0,-like slabs of MOO, octahedra connected by bridging MOO, tetrahedra. To date no analogous phosphate molybdenum bronzes have been found. Rather, a variety of insulating phosphate molybdenum oxides are known in which molybdenum displays well-defined valences of 5, 4 and even the very unusual 3. Mixed valence compounds are also seen, but they are quite different in structure from the PTBs. A few examples will illustrate these differences. (Reduced phosphate molybdenum oxides are reviewed in detail by Borel'.) Na,MoP,07 is an example of mixed valency in these systems where a range of non-stoichiometry also exists. A projection of the structure is shown in Figure 1. The building blocks are MOO, octahedra and P z 0 7 groups. The MOO, octahedra share corners with P,07 and are thus isolated in the structure, localizing all d electrons. In the process distorted octagonal and hexagonal tunnels form with the Na' ions residing in the octagonal tunnels off-center near the walls in sites that are partially occupied in a disordered fashion. In a stoichiometric trivalent NaMoP,O, phase with the NaFeP207 structure' layers of P207 groups connect isolated MOO, octahedra. Distorted octagonal cavities form in the Mo-0-P network where the Na' ions reside. Two different sites exist for Mo, one of which has Mo-0 bond distances much longer than might be expected for Mo(III), suggesting that it might be possible to detect the compound with respect to N a f and create a mixed valence compound. Small clusters of edge- and corner-sharing MOO, octahedra are found in several cesium molybdenum phosphates. These groups are separated from each other by
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Figure 1. Section of NaMoP,O, structure showing tunnels formed by the network of M o o 6 and P207groups; Na' ions are represented by the solid circles. (After Ref. 1.)
Figure 2. Cubanelike Mod04 clusters in Cs3Mo4P3OI6and their coordination by phosphate; Mo are solid circles; Cs is not shown. (After Ref. 4.)
mono-, di- and triphosphate groups. In Cs3Mo4P3OI6, large octagonal cavities where the Cs' ions reside are formed by edge-sharing M0404 clusters. These are connected to one another by monophosphate groups (Fig. 2). The Mo atoms in these clusters move
3.10.3.3 Tunnel Structure Oxides 239 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.5Siliconiobates, Silicotantalates, and Germanium Compounds off-center toward each other to form distorted tetrahedral cubanelike clusters in which Mo-Mo distances are 2.56 to 2.69 A3. Haushalter reported various microporous reduced molybdenum phosphates. One, [Et4N]6[Na14M024P17097(OH)31]~ H 2 0 , contains the complex cluster [Na12M024P17097(OH)31]8-, which can accommodate 12 Na' in octahedral coordination with a phosphoric acid molecule in the center. The clusters then link up through other Na' ions to form a three-dimensional structure that contains tunnels where the Me4N+ ions are found. This compound, prepared hydrothermally, rivals zeolites in its complexity and may have similar applications4. (M. GREENBLATT, B. RAVEAU) 1. M. M. Borel, Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 2. A. Leclaire, M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 78, 220 (1989). 3. R. Haushalter, J . Chem. Soc., Chem. Soc. Commun., 1567 (1987). 4. R. Haushalter, Angew. Chem., Int. Ed. Engl., 28, 793 (1989).
3.10.3.3.5.4 Other Reduced Transition Metal Phosphates. Mixed-valence transition metal phosphates have been found recently for Ti, V, Nb, and Mo. They are not discussed in detail here, but several examples are cited in Reference 1. Their crystal chemistry and properties are more closely related to those of the Mo analogues in that they have mixed frameworks of M 0 6 octahedra that are partially or wholly isolated from one another by intervening phosphate groups, and the d electrons do not appear to be delocalized. Phases of composition BaM2P4014(M3+ = Ti, V, Mo) have been found to contain MOB octahedra isolated by phosphate linkages2. A large number of mixed-valent vanadium phosphates have been prepared by hydrothermal techniques using organic templates. These materials have open framework structures with giant voids and may have applications as catalysts and/or ion exchange materials3. (M. GREENBLATT, 6.RAVEAU) 1. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 2. J. S. Wang, S. J. Hwu, J . Solid State Chem., 90, 31 (1991). 3. M. I. Khan, L. Meyer, R. C. Haushalter, A. L. Schweitzer, J. Zubieta, J. L. Dye, Chem. Mater., 8,
43 (1996).
3.10.3.3.5.5 Siliconiobates, Silicotantalates, and Corresponding Germanium Compounds. These compounds form a large family of tunnel structures'. The host lattice of the A6-xM6Si4026and A6-xM6Ge4026 oxides (Fig. 1) is formed from triple octahedral files sharing their corners with Si207 or Ge207 groups. This framework delimits pentagonal tunnels as in TTB where the A ions (K, Ba) are located. These phases are prepared by reaction of the carbonates A C 0 3 or A2CO3 with S i 0 2 or GeO, and M 2 0 5(M = Ta, Nb) in air for a wide range of nonstoichiometry (0 2 x 2 3). The Si207 or G e 2 0 7groups can be replaced by B 0 3 triangles, which allow connection between the triple octahedral files: e.g., K3M3B2012(M = Ta, Nb) oxides are easily synthesized by heating mixtures of B203, K 2 C 0 3 ,and M 2 0 5in air. The two-dimensional similarity of this structure to that of the A3M8OZ1 cage structures allows syntheses of multiple phases (A3M8021)n,which correspond to the intergrowth of A3M802, and A3M&026 slabs (see 3.10.3.2).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.3 Tunnel Structure Oxides 239 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.5Siliconiobates, Silicotantalates, and Germanium Compounds off-center toward each other to form distorted tetrahedral cubanelike clusters in which Mo-Mo distances are 2.56 to 2.69 A3. Haushalter reported various microporous reduced molybdenum phosphates. One, [Et4N]6[Na14M024P17097(OH)31]~ H 2 0 , contains the complex cluster [Na12M024P17097(OH)31]8-, which can accommodate 12 Na' in octahedral coordination with a phosphoric acid molecule in the center. The clusters then link up through other Na' ions to form a three-dimensional structure that contains tunnels where the Me4N+ ions are found. This compound, prepared hydrothermally, rivals zeolites in its complexity and may have similar applications4. (M. GREENBLATT, B. RAVEAU) 1. M. M. Borel, Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 2. A. Leclaire, M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 78, 220 (1989). 3. R. Haushalter, J . Chem. Soc., Chem. Soc. Commun., 1567 (1987). 4. R. Haushalter, Angew. Chem., Int. Ed. Engl., 28, 793 (1989).
3.10.3.3.5.4 Other Reduced Transition Metal Phosphates. Mixed-valence transition metal phosphates have been found recently for Ti, V, Nb, and Mo. They are not discussed in detail here, but several examples are cited in Reference 1. Their crystal chemistry and properties are more closely related to those of the Mo analogues in that they have mixed frameworks of M 0 6 octahedra that are partially or wholly isolated from one another by intervening phosphate groups, and the d electrons do not appear to be delocalized. Phases of composition BaM2P4014(M3+ = Ti, V, Mo) have been found to contain MOB octahedra isolated by phosphate linkages2. A large number of mixed-valent vanadium phosphates have been prepared by hydrothermal techniques using organic templates. These materials have open framework structures with giant voids and may have applications as catalysts and/or ion exchange materials3. (M. GREENBLATT, 6.RAVEAU) 1. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 2. J. S. Wang, S. J. Hwu, J . Solid State Chem., 90, 31 (1991). 3. M. I. Khan, L. Meyer, R. C. Haushalter, A. L. Schweitzer, J. Zubieta, J. L. Dye, Chem. Mater., 8,
43 (1996).
3.10.3.3.5.5 Siliconiobates, Silicotantalates, and Corresponding Germanium Compounds. These compounds form a large family of tunnel structures'. The host lattice of the A6-xM6Si4026and A6-xM6Ge4026 oxides (Fig. 1) is formed from triple octahedral files sharing their corners with Si207 or Ge207 groups. This framework delimits pentagonal tunnels as in TTB where the A ions (K, Ba) are located. These phases are prepared by reaction of the carbonates A C 0 3 or A2CO3 with S i 0 2 or GeO, and M 2 0 5(M = Ta, Nb) in air for a wide range of nonstoichiometry (0 2 x 2 3). The Si207 or G e 2 0 7groups can be replaced by B 0 3 triangles, which allow connection between the triple octahedral files: e.g., K3M3B2012(M = Ta, Nb) oxides are easily synthesized by heating mixtures of B203, K 2 C 0 3 ,and M 2 0 5in air. The two-dimensional similarity of this structure to that of the A3M8OZ1 cage structures allows syntheses of multiple phases (A3M8021)n,which correspond to the intergrowth of A3M802, and A3M&026 slabs (see 3.10.3.2).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3.3 Tunnel Structure Oxides 239 3.10.3.3.5 Complex Oxides with Host Lattice 3.1 0.3.3.5.5Siliconiobates, Silicotantalates, and Germanium Compounds off-center toward each other to form distorted tetrahedral cubanelike clusters in which Mo-Mo distances are 2.56 to 2.69 A3. Haushalter reported various microporous reduced molybdenum phosphates. One, [Et4N]6[Na14M024P17097(OH)31]~ H 2 0 , contains the complex cluster [Na12M024P17097(OH)31]8-, which can accommodate 12 Na' in octahedral coordination with a phosphoric acid molecule in the center. The clusters then link up through other Na' ions to form a three-dimensional structure that contains tunnels where the Me4N+ ions are found. This compound, prepared hydrothermally, rivals zeolites in its complexity and may have similar applications4. (M. GREENBLATT, B. RAVEAU) 1. M. M. Borel, Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 2. A. Leclaire, M. Borel, A. Grandin, B. Raveau, J . Solid State Chem., 78, 220 (1989). 3. R. Haushalter, J . Chem. Soc., Chem. Soc. Commun., 1567 (1987). 4. R. Haushalter, Angew. Chem., Int. Ed. Engl., 28, 793 (1989).
3.10.3.3.5.4 Other Reduced Transition Metal Phosphates. Mixed-valence transition metal phosphates have been found recently for Ti, V, Nb, and Mo. They are not discussed in detail here, but several examples are cited in Reference 1. Their crystal chemistry and properties are more closely related to those of the Mo analogues in that they have mixed frameworks of M 0 6 octahedra that are partially or wholly isolated from one another by intervening phosphate groups, and the d electrons do not appear to be delocalized. Phases of composition BaM2P4014(M3+ = Ti, V, Mo) have been found to contain MOB octahedra isolated by phosphate linkages2. A large number of mixed-valent vanadium phosphates have been prepared by hydrothermal techniques using organic templates. These materials have open framework structures with giant voids and may have applications as catalysts and/or ion exchange materials3. (M. GREENBLATT, 6.RAVEAU) 1. M. M. Borel, M. Goreaud, A. Grandin, P. Labbe, A. Leclaire, B. Raveau, Eur. J . Solid State Inorg. Chem., 28, 93 (1991). 2. J. S. Wang, S. J. Hwu, J . Solid State Chem., 90, 31 (1991). 3. M. I. Khan, L. Meyer, R. C. Haushalter, A. L. Schweitzer, J. Zubieta, J. L. Dye, Chem. Mater., 8,
43 (1996).
3.10.3.3.5.5 Siliconiobates, Silicotantalates, and Corresponding Germanium Compounds. These compounds form a large family of tunnel structures'. The host lattice of the A6-xM6Si4026and A6-xM6Ge4026 oxides (Fig. 1) is formed from triple octahedral files sharing their corners with Si207 or Ge207 groups. This framework delimits pentagonal tunnels as in TTB where the A ions (K, Ba) are located. These phases are prepared by reaction of the carbonates A C 0 3 or A2CO3 with S i 0 2 or GeO, and M 2 0 5(M = Ta, Nb) in air for a wide range of nonstoichiometry (0 2 x 2 3). The Si207 or G e 2 0 7groups can be replaced by B 0 3 triangles, which allow connection between the triple octahedral files: e.g., K3M3B2012(M = Ta, Nb) oxides are easily synthesized by heating mixtures of B203, K 2 C 0 3 ,and M 2 0 5in air. The two-dimensional similarity of this structure to that of the A3M8OZ1 cage structures allows syntheses of multiple phases (A3M8021)n,which correspond to the intergrowth of A3M802, and A3M&026 slabs (see 3.10.3.2).
240
3.10 Formation of Non-stoichiometricOxides 3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.4 Adaptive Structures h
C
Figure 1. The structure of A6-xM6Si4026:the host lattice built from M 0 6 octahedra and Si20, groups. (After Ref. 1.) Distorted hexagonal tunnels are also observed for oxides of the Ga203-TiOz system2, but they are empty, e.g., in Ga4Ti21048and Ga4Ti08,whose host lattices may be related to those of hollandite, rutile, and P-Ga203. (M. GREENBLATT, B. RAVEAU) 1. B. Raveau, Reo. Inorg. Chem., I, 81 (1979). 2. L. A. Bursill, A m Crystallogr., Sect. B, 35, 530 (1979).
3.10.3.4 Adaptive Structures
The term “infinitely adaptive” structures was first applied to nonstoichiometric oxides’ in an attempt to systematize a group of particularly poorly characterized substances. These oxides exhibit several poorly understood phenomena. First, the exact crystal structures are not known, partially because single crystals are difficult to obtain but more importantly because in all cases there are superstructure diffraction effects that are incommensurate, or nonintegral. Although some other compounds may exhibit incommensurate diffraction, adaptive structures show a continuous variation of the incommensurate diffraction over a wide range of temperature and/or composition. Oxide phases with demonstrated infinitely adaptive structures include phases in the systems Y2O3-YF3’ and other similar oxide fluorides with the smaller rare earth ions from about Gd3+ to Lu3+ (see 3.10.3.5.1),Zr02-Nb20s, Zr02-Ta20,3,4(see 3.10.3.4.1), Ta2OSs, and solid solutions of TazOS with aliovalent cations of intermediate radii6 (namely those that generally occur in octahedral coordination: see 3.10.3.4.2),and other phases with the low-Ta,O5-type structure such as Nb2OSunder high pressure7 and the system U205-U308s(see 3.10.3.4.3). Adaptive structures also occur in other nonoxide systems (e.g., Bi2Te3-BiTe)g and probably are much more prevalent than generally
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 240
3.10 Formation of Non-stoichiometricOxides 3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.4 Adaptive Structures h
C
Figure 1. The structure of A6-xM6Si4026:the host lattice built from M 0 6 octahedra and Si20, groups. (After Ref. 1.) Distorted hexagonal tunnels are also observed for oxides of the Ga203-TiOz system2, but they are empty, e.g., in Ga4Ti21048and Ga4Ti08,whose host lattices may be related to those of hollandite, rutile, and P-Ga203. (M. GREENBLATT, B. RAVEAU) 1. B. Raveau, Reo. Inorg. Chem., I, 81 (1979). 2. L. A. Bursill, A m Crystallogr., Sect. B, 35, 530 (1979).
3.10.3.4 Adaptive Structures
The term “infinitely adaptive” structures was first applied to nonstoichiometric oxides’ in an attempt to systematize a group of particularly poorly characterized substances. These oxides exhibit several poorly understood phenomena. First, the exact crystal structures are not known, partially because single crystals are difficult to obtain but more importantly because in all cases there are superstructure diffraction effects that are incommensurate, or nonintegral. Although some other compounds may exhibit incommensurate diffraction, adaptive structures show a continuous variation of the incommensurate diffraction over a wide range of temperature and/or composition. Oxide phases with demonstrated infinitely adaptive structures include phases in the systems Y2O3-YF3’ and other similar oxide fluorides with the smaller rare earth ions from about Gd3+ to Lu3+ (see 3.10.3.5.1),Zr02-Nb20s, Zr02-Ta20,3,4(see 3.10.3.4.1), Ta2OSs, and solid solutions of TazOS with aliovalent cations of intermediate radii6 (namely those that generally occur in octahedral coordination: see 3.10.3.4.2),and other phases with the low-Ta,O5-type structure such as Nb2OSunder high pressure7 and the system U205-U308s(see 3.10.3.4.3). Adaptive structures also occur in other nonoxide systems (e.g., Bi2Te3-BiTe)g and probably are much more prevalent than generally
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.4 Adaptive Structures 3.10.3.4.1 Oxides with Vernier-Type Adaption Structures
24 1
thought. Many nonstoichiometric systems can be described in this manner if proper attention is given to the real nature of the diffraction data (see, e.g., the mullitelike compositions in the system Al2O3-SiOZ1’ and probably in B203-A1203-Si02). (R. S.ROTH) 1. J. S. Anderson, J. Chem. SOC.,Dalton Trans., 1107 (1973). 2. D. J. M. Bevan, in Solid State Chemistry, R. S. Roth, S. J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 749. 3. R. S. Roth, J. L. Waring, W. S. Brower, H. S. Parker, in Solid State Chemistry, R. S. Roth, S . J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 195. 4. J. Galy, R. S. Roth, J. Solid State Chern., 7, 277 (1973). 5. R. S. Roth, J. L. Waring, H. S. Parker, J. Solid State Chem., 2, 445 (1970). 6. R. S. Roth, J. L. Waring, J . Res. Natl. Bur. Stand., 74A, 485 (1970). 7. J. L. Waring, R. S. Roth, H. S. Parker, J. Res. Natl. Bur. Stand., 77A, 705 (1973). 8. A. F. Andersen, Acta Crystallogr., 11, 612 (1958). 9. R. F. Brebrick, in The Chemistry of Extended Defects in Non-Metallic Solids, L. Eyring, M. O’Keeffe, eds., North-Holland, Amsterdam, 1970, p. 183. 10. R. Sadanaga, Y. Takeuchi, N. Morimoto, in Recent Progress ofNatural Sciences in Japan, Vol. 3, Yamamoto Printing Co., Tokyo, 1978, p. 141.
3.10.3.4.1 Oxides with Vernier-Type Adaption Structures
The term “uernier-type adaptive” was first used’ to describe the structure of continuously varying incommensurate diffraction phases’ found in the system Y203-YF3. It was also applied to interpretation of phase structures in the systems Nb205-Zr02 and Ta205-Zr02334, which show very similar diffraction patterns. However, in the zirconiabased phases, these compounds, which are no longer just superstoichiometric fluoritetype structures, have the N b 5 + or T a S Cions in octahedral coordination. This “pins” the vernier movement of the anion/cation layers and gives rise to what is termed a “pinned vernier” structure. It is uncertain that there is any real difference between “vernier type” and “continuously adaptive” structures. All adaptive structures may be, more or less, due to a vernier-type mechanism. An adaptive or vernier structure is characterized by having at least one direction in the unit cell that varies continuously from one simple multiple value of the subcell through several other simple values across a compositional region. If either end member has a truly commensurate simple multiple of the subcell, it is referred to as a “locked-in’’ value. This “locked-in’’ structure may, or may not, have a reasonable structural interpretation. An orthorhombic phase having an X-ray diffraction powder pattern related to a distorted fluorite or an a-Pb02-typestructure occurs in the systems Nb,O,-ZrO, and Ta20,-Zr02 at a composition near Me2Zr601,315(Fig. 1).It was later shown3 that this phase has satellite peaks in the single crystal diffraction patterns that vary with composition (Fig. 2). All satellite peaks of the modulated structure lie along the b* axis and cause a multiplication the unit cell varying from approximately seven times the subcell to exactly 10 times the subcell (the latter has a value of 51.18 A). This value, apparently a “locked-in” structure, is represented by the formula Nb2Zr,0zl. Single crystals of the Nd-Zr oxide and Ta-Zr oxide phases with various pentavalent-tetravalent cation ratios were grown from a Ba0-V205 flux3. The structure of the composition Nb2Zr6O1,, with a multiplicity of 8 times the subcell was analyzed by single-crystal diffraction4 (Fig. 3), and a hypothesis was advanced to explain the
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.4 Adaptive Structures 3.10.3.4.1 Oxides with Vernier-Type Adaption Structures
24 1
thought. Many nonstoichiometric systems can be described in this manner if proper attention is given to the real nature of the diffraction data (see, e.g., the mullitelike compositions in the system Al2O3-SiOZ1’ and probably in B203-A1203-Si02). (R. S.ROTH) 1. J. S. Anderson, J. Chem. SOC.,Dalton Trans., 1107 (1973). 2. D. J. M. Bevan, in Solid State Chemistry, R. S. Roth, S. J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 749. 3. R. S. Roth, J. L. Waring, W. S. Brower, H. S. Parker, in Solid State Chemistry, R. S. Roth, S . J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 195. 4. J. Galy, R. S. Roth, J. Solid State Chern., 7, 277 (1973). 5. R. S. Roth, J. L. Waring, H. S. Parker, J. Solid State Chem., 2, 445 (1970). 6. R. S. Roth, J. L. Waring, J . Res. Natl. Bur. Stand., 74A, 485 (1970). 7. J. L. Waring, R. S. Roth, H. S. Parker, J. Res. Natl. Bur. Stand., 77A, 705 (1973). 8. A. F. Andersen, Acta Crystallogr., 11, 612 (1958). 9. R. F. Brebrick, in The Chemistry of Extended Defects in Non-Metallic Solids, L. Eyring, M. O’Keeffe, eds., North-Holland, Amsterdam, 1970, p. 183. 10. R. Sadanaga, Y. Takeuchi, N. Morimoto, in Recent Progress ofNatural Sciences in Japan, Vol. 3, Yamamoto Printing Co., Tokyo, 1978, p. 141.
3.10.3.4.1 Oxides with Vernier-Type Adaption Structures
The term “uernier-type adaptive” was first used’ to describe the structure of continuously varying incommensurate diffraction phases’ found in the system Y203-YF3. It was also applied to interpretation of phase structures in the systems Nb205-Zr02 and Ta205-Zr02334, which show very similar diffraction patterns. However, in the zirconiabased phases, these compounds, which are no longer just superstoichiometric fluoritetype structures, have the N b 5 + or T a S Cions in octahedral coordination. This “pins” the vernier movement of the anion/cation layers and gives rise to what is termed a “pinned vernier” structure. It is uncertain that there is any real difference between “vernier type” and “continuously adaptive” structures. All adaptive structures may be, more or less, due to a vernier-type mechanism. An adaptive or vernier structure is characterized by having at least one direction in the unit cell that varies continuously from one simple multiple value of the subcell through several other simple values across a compositional region. If either end member has a truly commensurate simple multiple of the subcell, it is referred to as a “locked-in’’ value. This “locked-in’’ structure may, or may not, have a reasonable structural interpretation. An orthorhombic phase having an X-ray diffraction powder pattern related to a distorted fluorite or an a-Pb02-typestructure occurs in the systems Nb,O,-ZrO, and Ta20,-Zr02 at a composition near Me2Zr601,315(Fig. 1).It was later shown3 that this phase has satellite peaks in the single crystal diffraction patterns that vary with composition (Fig. 2). All satellite peaks of the modulated structure lie along the b* axis and cause a multiplication the unit cell varying from approximately seven times the subcell to exactly 10 times the subcell (the latter has a value of 51.18 A). This value, apparently a “locked-in” structure, is represented by the formula Nb2Zr,0zl. Single crystals of the Nd-Zr oxide and Ta-Zr oxide phases with various pentavalent-tetravalent cation ratios were grown from a Ba0-V205 flux3. The structure of the composition Nb2Zr6O1,, with a multiplicity of 8 times the subcell was analyzed by single-crystal diffraction4 (Fig. 3), and a hypothesis was advanced to explain the
1750
0 10 Nb*O,
1550
1600
1650
20
(a)
40 50 60 70 COMPOSITION, MOL %
30
80 90
100 ZrO,
1500
1550
1600
Figure 1. (a) Suggested equilibrium diagram for Nb2O5-ZrOZ5:S.S., solid solution. (b) Proposed phase equilibrium diagram of a portion of the system NbzO5-ZrO2. (After Ref. 3.)
z
f
l-
a
2 1700
LT
u-
9
1950
3.10.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.4 Adaptive Structures 3.10.3.4.1 Oxides with Vernier-Type Adaption Structures (OK01
Nb,O,:ZrO,
243
m
64 60 54
34 30 26
1.T
15
34 32 30
4’ 0 4
2:11
I’
0
8 17
I’
2:13
9 19 42 4038
4.1
2:15
I 20
10
I 15
mm
I
I
10
5
Mob RADIATION
Figure 2. Diagrammatic representation of the left-hand portion of the (oko) level of single-crystal precession patterns of the orthorhombic phase(s) with superstructure of 15, 8, 17, and 10 times the subcell. This illustrates how the superstructure spots approach the subcell spot as the composition approaches ZrO,. (After Ref. 3.) X
t-
zI
Figure 3. Representation, at one level, of the refined structure of NbzZr,Ol, as polyhedra linked together by edge- and corner-sharing (metal atoms approximately at y = 0). The “apparently isolated” octahedra are actually edge-shared with the sevenfold coordinated polyhedra of the adjacent unit cell, as shown in the postulated structure of m = 6. (After Ref. 4.) structures of the other integral values of the multiplicity on the basis of packing of polyhedra (Fig. 4). Although this structural description is adequate for discrete phases, it does not give a believable picture for the increasingly larger values needed to describe the structure of an intermediate composition.
244
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.4 Adaptive Structures 3.10.3.4.1 Oxides with Vernier-Type Adaption Structures
m= 4
m = 6
m= 8
m=IO
Figure 4. Polyhedral representations of the proposed structures for phases in the homologous series M n 0 2 n + with l n = 4, 6, 8, and 10, based on the structure of Nb2Zr6017 (m = 8). The m = 10 diagram is the proposed structure of Nb2Zr8021and m = 6 is the proposed structure of Y605F8.The “apparently isolated” octahedra are actually edgeshared with the sevenfold coordinated polyhedra of the adjacent unit cell, as shown in the postulated structure of m = 6. (After Ref. 4.)
Since there are no two-phase regions in this type of solid solution, we must look elsewhere for an explanation of a modulated structure. This phase has been integrated as a vernier structure‘, in which the oxygen and cation networks do not quite fit each other, giving rise to longer and longer distances needed before repetition of the misfit pattern. This concept eliminates the need for ultra-long-range ordering for the intermediate (nonintegral) members of the solid solution. The structural variations in the Nb,Zr,O, type phases can best be understood with reference to a vernier-type mechanism, as is the case for the yttrium oxyfluorides, manganese silicides, and other similar phases6.
,-
(R.
S.ROTH)
1. G. Hyde, A. N. Bagshaw, S. Andersson, M. O’Keeffe, Annu. Reo. Muter. Sci.,4, 43 (1974). 2. J. M. Bevan, in Solid State Chemistry, R. S. Roth, S . J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 749.
3.10.3 ODerationallv NonstoichiometricOxide Phases 245 3.10.3.4 Adaptive Structures 3.10.3.4.2 Double Oxides Based on Tantalum Pentoxide and Related Phases 3. R. S. Roth, J. L. Waring, W. S. Brower, H. S. Parker, in Solid State Chemistry, R. S. Roth, S. J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 183. 4. J. Galy, R. S. Roth, J . Solid State Chem., 7, 277 (1973). 5. R. S. Roth, L. W. Coughanour, J . Res. U.S. Natl. Bur. Stand., 55, 209, RP2621 (1955). 6. R. S. Roth, Prog. Solid State Chem., 13, 159 (1981). 3.10.3.4.2 Double Oxides Based on Tantalum Pentoxide and Related Phases
Tantalum pentoxide exists as at least two completely different polymorphs. A quenchable phase transformation occurs in TazO5 at 1360 & 10°C’. Pure Ta2O5, when heated and quenched from above this transition, has a high temperature triclinic form at RT but goes through two minor symmetry changes, metastably, at 320°C to monoclinic and at 920°C to tetragonal’. This high temperature form is stabilized by many transition elements and, in fact, by all the aliovalent ions that ordinarily occur in octahedral coordination: Sn4+,Ga3+,Cr3+,Fe3+,Sc3+,and Mg213. The crystal structure of the scandium-doped high temperature form was described4 as a variant of the shear structure types, but with mixed octahedral and hexagonal-bipyrimidal coordination. However, the low temperature form of Ta2O5 apparently exists in an infinitely adaptive form with superstructure peaks that vary systematically not only with impurity concentration but also with heat treatment of almost any given compositional ~ a r i a n t ~The , ~ Ta5+ . ion is one of the few transition element ions known in only one oxidation state. TaZO, apparently exists in equilibrium with metallic Ta. Nonstoichiometric T a 2 0 5can be prepared only by melting the oxide in Ta metal and metastably quenching the eutectic composition that forms. All reports of a rutile-type T a 0 2 are apparently due to erroneous identification of TaON as an oxide. TazO5 can be formed by hydrolyzation of a solution prepared, e.g., by dissolving Ta metal in hot HF. Precipitated Ta2O5 is generally amorphous but crystallizes quickly into an apparently orthorhombic, poorly crystalline variety. As this material is heated at increasingly higher temperatures, and/or for longer periods of time, the X-ray diffraction pattern gradually changes. For materials quenched from 1350°C, apparent superstructure lines can be indexed on the basis of a unit cell with a multiplicity along the b axis of 11 times the subcell. Below 1350”C,the d values of the superstructure peaks in the X-ray diffraction pattern gradually shift as the specimen approaches equilibrium, regardless of whether the specimen had been heated to higher temperatures. To obtain equilibrium values, the specimen must be quenched from the temperature under study, since slow cooling tends to shift the peaks in the diffraction pattern toward values that would occur at lower temperature equilibrium. At low temperatures, Ta205 apparently kinetically approaches a structure with a multiplicity of the b axis equal to about 14. At all intermediate temperatures the low temperature polymorph or have polymorphs a “continuously adaptive” structure that continuously varies between the m = 14 and the m = 11 “locked-in’’ values of the superstructure6. The adaptive structures of the low temperature polymorph(s) of TaZO5 can be strongly affected by addition of smaller aliovalent ions. Addition of Mo6+,W 6 + ,Si4+, Ge4+, Zr4+, Ti4’, B3+,A13+,6and Li+ oxides affects the multiplicity of the subcell differently in each case. The W 0 3 , SOz, GeOz, BZO3, A1203, and LizO form phases similar to the low temperature form which are stable up to the solidus temperatures of the corresponding systems. These solid solutions of various oxides in Ta205 are synthesized by appropriate mixtures of two (or more) oxides heated together to 1000-1800°C. If the second oxide is volatile, sealed Pt tubes are required.
’
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 ODerationallv NonstoichiometricOxide Phases 245 3.10.3.4 Adaptive Structures 3.10.3.4.2 Double Oxides Based on Tantalum Pentoxide and Related Phases 3. R. S. Roth, J. L. Waring, W. S. Brower, H. S. Parker, in Solid State Chemistry, R. S. Roth, S. J. Schneider, eds., NBS Special Publication 364, National Bureau of Standards, Washington, DC, 1972, p. 183. 4. J. Galy, R. S. Roth, J . Solid State Chem., 7, 277 (1973). 5. R. S. Roth, L. W. Coughanour, J . Res. U.S. Natl. Bur. Stand., 55, 209, RP2621 (1955). 6. R. S. Roth, Prog. Solid State Chem., 13, 159 (1981). 3.10.3.4.2 Double Oxides Based on Tantalum Pentoxide and Related Phases
Tantalum pentoxide exists as at least two completely different polymorphs. A quenchable phase transformation occurs in TazO5 at 1360 & 10°C’. Pure Ta2O5, when heated and quenched from above this transition, has a high temperature triclinic form at RT but goes through two minor symmetry changes, metastably, at 320°C to monoclinic and at 920°C to tetragonal’. This high temperature form is stabilized by many transition elements and, in fact, by all the aliovalent ions that ordinarily occur in octahedral coordination: Sn4+,Ga3+,Cr3+,Fe3+,Sc3+,and Mg213. The crystal structure of the scandium-doped high temperature form was described4 as a variant of the shear structure types, but with mixed octahedral and hexagonal-bipyrimidal coordination. However, the low temperature form of Ta2O5 apparently exists in an infinitely adaptive form with superstructure peaks that vary systematically not only with impurity concentration but also with heat treatment of almost any given compositional ~ a r i a n t ~The , ~ Ta5+ . ion is one of the few transition element ions known in only one oxidation state. TaZO, apparently exists in equilibrium with metallic Ta. Nonstoichiometric T a 2 0 5can be prepared only by melting the oxide in Ta metal and metastably quenching the eutectic composition that forms. All reports of a rutile-type T a 0 2 are apparently due to erroneous identification of TaON as an oxide. TazO5 can be formed by hydrolyzation of a solution prepared, e.g., by dissolving Ta metal in hot HF. Precipitated Ta2O5 is generally amorphous but crystallizes quickly into an apparently orthorhombic, poorly crystalline variety. As this material is heated at increasingly higher temperatures, and/or for longer periods of time, the X-ray diffraction pattern gradually changes. For materials quenched from 1350°C, apparent superstructure lines can be indexed on the basis of a unit cell with a multiplicity along the b axis of 11 times the subcell. Below 1350”C,the d values of the superstructure peaks in the X-ray diffraction pattern gradually shift as the specimen approaches equilibrium, regardless of whether the specimen had been heated to higher temperatures. To obtain equilibrium values, the specimen must be quenched from the temperature under study, since slow cooling tends to shift the peaks in the diffraction pattern toward values that would occur at lower temperature equilibrium. At low temperatures, Ta205 apparently kinetically approaches a structure with a multiplicity of the b axis equal to about 14. At all intermediate temperatures the low temperature polymorph or have polymorphs a “continuously adaptive” structure that continuously varies between the m = 14 and the m = 11 “locked-in’’ values of the superstructure6. The adaptive structures of the low temperature polymorph(s) of TaZO5 can be strongly affected by addition of smaller aliovalent ions. Addition of Mo6+,W 6 + ,Si4+, Ge4+, Zr4+, Ti4’, B3+,A13+,6and Li+ oxides affects the multiplicity of the subcell differently in each case. The W 0 3 , SOz, GeOz, BZO3, A1203, and LizO form phases similar to the low temperature form which are stable up to the solidus temperatures of the corresponding systems. These solid solutions of various oxides in Ta205 are synthesized by appropriate mixtures of two (or more) oxides heated together to 1000-1800°C. If the second oxide is volatile, sealed Pt tubes are required.
’
246
Figure 1. Phase equilibrium diagram for a portion of the Taz05-W03* system, revised to show the low-Ta,O,-type phase as a solid solution region.
a
Figure 2. Projection of the proposed Ta30W2081structure onto the (001) plane. Distortion planes (containing postulated oxygen vacancies) obey the symmetry of the plane group pm. Dots represent metal atoms; shaded areas are oxygen coordinated polyhedra. (From Re[. 10.)
-1
247
248
Figure 3. Proposed crystal structure of the Ta205,m = 11 low temperature polymorph. (From Ref. 10.)
I
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.4 Adaptive Structures 3.10.3.4.3 The Metal Uranates and Related Oxides
249
All these oxides, except Li20, cause the apparent superstructure to shift continuously from m = 11 toward m = 8 or even toward (but never quite equal to) m = 5. For wo38,9 (Fig. l), the composition 15Ta2O5: 2 W 0 3 has a superstructure exactly equal to m = 8 and also corresponds to a maximum on the melting curve. It might be no coincidence that this is a very stable configuration. This phase structure was analyzed" along with other compositions in the system (Fig. 2), but the conclusion of ordered oxygen vacancies may be incorrect. The direction of the superstructure movement is probably more related to effective ionic radii of the admixture than to cation/anion ratio, since A1203 causes the same type of movement as W 0 3 6but Z r 0 2 causes a movement in the opposite direction. Only L i 2 0 goes into solid solution in T a 2 0 5 ' with no apparent change in the superstructure. Large single crystals of this m = 11 superstructure phase (Fig. 3) with a composition of about 6.5 mol % L i 2 0 have been grown directly from the melt and were examined by neutron diffraction single-crystal analysis". These data failed to confirm the oxygen vacancy hypothesis but did not lead to a unique solution to the structure. High resolution electron microscope lattice images and electron diffraction patterns12 seem to indicate an incommensurate superstructure in the c-axis direction, as well as the more obvious b-axis direction of the adaptive structure. The high pressure form of N b 2 0 5at about 100,000 psi and > 1000°C has a structure similar to m = 813, and various uranium oxides from about U 2 0 5 to U 3 0 8 also have a similar superstr~cture'~. (R. S.ROTH) 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.
A. Reisman, F. Holtzberg, M. Berkenblit, M. Berry, J . Am. Chem. Soc., 78, 4514 (1956). J. L. Waring, R. S. Roth, J . Res. U.S. Natl. Bur. Stand., 72A, 175 (1968). R. S. Roth, J. L. Waring, W. S. Brower, J . Res. U S . Natl. Bur. Stand., 74A, 417 (1970) N. C. Stephenson, R. S. Roth, J . Solid State Chem., 3, 145 (1971). R. S. Roth, J. L. Waring, H. S. Parker, J . Solid State Chem., 2, 445 (1970). R. S. Roth, J. L. Waring, J . Res. U.S. Natl. Bur. Stand., 74A, 485 (1970). R. S. Roth, H. S. Parker, W. S. Brower, J. L. Waring, in Fast Ion Transport in Solids, W. Van Gool, ed., North-Holland, Amsterdam, 1973, p. 217. R. S. Roth, J. L. Waring, H. S. Parker, J . Solid State Chem., 2, 445 (1970). R. S . Roth, N. C. Stephenson, The Chemistry of Extended Defects in Non-Metallic Solids, L. Eyring, M. O'Keeffe, eds., North-Holland, Amsterdam, 1970, p. 167. N . C. Stephenson, R. S. Roth, Acta Crystallogr., Sect B, 27, 1010 (1971). R. S. Roth, E. Prince, in Difraction Studies ofReal Atoms and Real Crystals, Australian Academy of Science, Sydney, 1974, p. 197. S. Iijima, Proc. Annu. Meeting Election Microsc. Soc. Am., 35, 188 (1977). J. L. Waring, R. S. Roth, H. S. Parker, J . Res. U.S. Natl. Bur. Stand., 77A, 705 (1973). A. F. Andresen, Acta Crystallogr., 11, 612 (1958).
3.10.3.4.3 The Metal Uranates and Related Oxides
Uranium forms many nonstoichiometric oxides. Fusion of these with alkali metal or alkaline earth carbonates (700- lO0OT) provides a correspondingly extensive series of metal uranates'. Identical uranates are prepared by fusion of the alkali carbonates with appropriate mixtures of U 0 3 and U 3 0 8 , e.g.:
+ Na2CO3-+Na2U2O7 + C 0 2 U 0 3 + U 3 0 8 + Li2C03-LizU4012 + C 0 2 2U03
(a) (b)
Thermal decomposition of metal salts of the uranyl acetate anion also yields many of these compositions.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.10.3 Operationally NonstoichiometricOxide Phases 3.10.3.4 Adaptive Structures 3.10.3.4.3 The Metal Uranates and Related Oxides
249
All these oxides, except Li20, cause the apparent superstructure to shift continuously from m = 11 toward m = 8 or even toward (but never quite equal to) m = 5. For wo38,9 (Fig. l), the composition 15Ta2O5: 2 W 0 3 has a superstructure exactly equal to m = 8 and also corresponds to a maximum on the melting curve. It might be no coincidence that this is a very stable configuration. This phase structure was analyzed" along with other compositions in the system (Fig. 2), but the conclusion of ordered oxygen vacancies may be incorrect. The direction of the superstructure movement is probably more related to effective ionic radii of the admixture than to cation/anion ratio, since A1203 causes the same type of movement as W 0 3 6but Z r 0 2 causes a movement in the opposite direction. Only L i 2 0 goes into solid solution in T a 2 0 5 ' with no apparent change in the superstructure. Large single crystals of this m = 11 superstructure phase (Fig. 3) with a composition of about 6.5 mol % L i 2 0 have been grown directly from the melt and were examined by neutron diffraction single-crystal analysis". These data failed to confirm the oxygen vacancy hypothesis but did not lead to a unique solution to the structure. High resolution electron microscope lattice images and electron diffraction patterns12 seem to indicate an incommensurate superstructure in the c-axis direction, as well as the more obvious b-axis direction of the adaptive structure. The high pressure form of N b 2 0 5at about 100,000 psi and > 1000°C has a structure similar to m = 813, and various uranium oxides from about U 2 0 5 to U 3 0 8 also have a similar superstr~cture'~. (R. S.ROTH) 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.
A. Reisman, F. Holtzberg, M. Berkenblit, M. Berry, J . Am. Chem. Soc., 78, 4514 (1956). J. L. Waring, R. S. Roth, J . Res. U.S. Natl. Bur. Stand., 72A, 175 (1968). R. S. Roth, J. L. Waring, W. S. Brower, J . Res. U S . Natl. Bur. Stand., 74A, 417 (1970) N. C. Stephenson, R. S. Roth, J . Solid State Chem., 3, 145 (1971). R. S. Roth, J. L. Waring, H. S. Parker, J . Solid State Chem., 2, 445 (1970). R. S. Roth, J. L. Waring, J . Res. U.S. Natl. Bur. Stand., 74A, 485 (1970). R. S. Roth, H. S. Parker, W. S. Brower, J. L. Waring, in Fast Ion Transport in Solids, W. Van Gool, ed., North-Holland, Amsterdam, 1973, p. 217. R. S. Roth, J. L. Waring, H. S. Parker, J . Solid State Chem., 2, 445 (1970). R. S . Roth, N. C. Stephenson, The Chemistry of Extended Defects in Non-Metallic Solids, L. Eyring, M. O'Keeffe, eds., North-Holland, Amsterdam, 1970, p. 167. N . C. Stephenson, R. S. Roth, Acta Crystallogr., Sect B, 27, 1010 (1971). R. S. Roth, E. Prince, in Difraction Studies ofReal Atoms and Real Crystals, Australian Academy of Science, Sydney, 1974, p. 197. S. Iijima, Proc. Annu. Meeting Election Microsc. Soc. Am., 35, 188 (1977). J. L. Waring, R. S. Roth, H. S. Parker, J . Res. U.S. Natl. Bur. Stand., 77A, 705 (1973). A. F. Andresen, Acta Crystallogr., 11, 612 (1958).
3.10.3.4.3 The Metal Uranates and Related Oxides
Uranium forms many nonstoichiometric oxides. Fusion of these with alkali metal or alkaline earth carbonates (700- lO0OT) provides a correspondingly extensive series of metal uranates'. Identical uranates are prepared by fusion of the alkali carbonates with appropriate mixtures of U 0 3 and U 3 0 8 , e.g.:
+ Na2CO3-+Na2U2O7 + C 0 2 U 0 3 + U 3 0 8 + Li2C03-LizU4012 + C 0 2 2U03
(a) (b)
Thermal decomposition of metal salts of the uranyl acetate anion also yields many of these compositions.
250 3.10 Formation of Non-stoichiometric Oxides 3.1 0.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.5 Mixed Valence, Mixed Anion Phases, Including Oxides with Cations
Discrete anions of uranium are not found in the alkali metal and alkaline earth uranates. Even apparently normal compounds such as N a 2 U 0 4 contain infinite twodimensional anion chains with two different U-0 distances. SrU0, and BaUO, have infinite chains of distorted U 0 6 octahedra in a rutile-type structure with two short U-0 bonds and four longer bonds2. Although some stoichiometric compositions emerge (e.g., Rb2U4013),a wide, essentially continuous N a 2 U 0 4 ,Na6U702,, N a 2 U 2 0 7 CszUl , range of compositions is available. (L. E. CONROY)
1. E. H. P. Cordfunke, B. 0. Loopstra, J . Inorg. Nucl. Chem., 33, 2427 (1971). 2. A. F. Wells, Structural Inorganic Chemistry, Clarendon Press, Oxford, 1975, p. 1003.
3.10.3.5 Mixed Valence, Mixed Anion Phases, Including Oxides with Cations of Variable Valence (or Mixed Cations) Balanced by Substitution of Altervalent Anions Nonstoichiometric compositions in oxide phases can occur by substitution of monovalent anions, typically halide or hydroxide, for oxide anions. One class of such oxyhalides involves replacement of oxide ions by twice the number of halide ions, so that no formal metal cation valence change occurs. Many group IIIA element examples occur. The yttrium oxyfluoride system is a particularly well-characterized example (see 3.10.3.5.1).A second class of mixed anion nonstoichiometric oxides involves one-for-one replacement of oxide anions by monovalent anions, resulting in a decrease in the formal positive valence of a corresponding number of cations. Oxyfluoride phases with the ReO, structure of the type M 0 3 -,F, illustrate this class of nonstoichiometry' - 4 . Substitution of the monovalent halide anion for the divalent oxide anion introduces another electron into the band structure of the solid. In the cases of MO and W oxide systems M o o 3-xFx and WO,-,F,, the extra electron goes into a conduction band so that the phases are metallic conductors with ranges of colors and luster. The similarities to the M O and W bronzes, for which these compounds are the exact electronic analogues, is striking. Among the N b and Ta oxyfluorides, the compositions M 0 3-,F, vary in values of x from 1 to nearly 3 in a continuous series3. All phases exist in the R e 0 3 structure, wherein the metal atom is in octahedral coordination with six 0 atoms. In the ideal R e 0 3 structure, the oxygens lie at the midpoint of the line connecting adjacent Re atoms, but the structure will accommodate distortions from that symmetry. The oxyfluorides are prepared5 by heating the metal trioxides, the metal, and H F in sealed gold capsules at 700°C and 3 kbar for 8 h. Under these conditions, Mo03-,F, compositions form with a maximum value of x = 0.66. Compositions with 0.74 < x < 0.97 had the cubic R e 0 3 structure. The W 0 3-,F, system ranged to a maximum value of x = 0.66 with the cubic R e 0 3 structure occurring in the range 0.17 < x < 0.66. (L. E. CONROY)
1. D. Bable, in Structure and Bonding, Vol. 111, C. K. Jorgensen, ed., Springer-Verlag, New York,
1967, p. 31. 2. K. Vorres, J. Donohue, Acta Crystallogr., 8, 25 (1955). 3. H. Schafer, H. G. Schnering, K. J. Niehues, H. G. Nieder-Vaharenholz, J . Less-Common Met., 9, 95 (1965). 4. D. E. LaValle, R. M. Steele, M. K. Wilkinson, H. L. Yakel, J . Am. Chem. Soc., 82, 2433 (1960). 5. A. W. Sleight, Inorg. Chem., 8, 1964 (1969).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
250 3.10 Formation of Non-stoichiometric Oxides 3.1 0.3 Operationally Nonstoichiometric Oxide Phases 3.10.3.5 Mixed Valence, Mixed Anion Phases, Including Oxides with Cations
Discrete anions of uranium are not found in the alkali metal and alkaline earth uranates. Even apparently normal compounds such as N a 2 U 0 4 contain infinite twodimensional anion chains with two different U-0 distances. SrU0, and BaUO, have infinite chains of distorted U 0 6 octahedra in a rutile-type structure with two short U-0 bonds and four longer bonds2. Although some stoichiometric compositions emerge (e.g., Rb2U4013),a wide, essentially continuous N a 2 U 0 4 ,Na6U702,, N a 2 U 2 0 7 CszUl , range of compositions is available. (L. E. CONROY)
1. E. H. P. Cordfunke, B. 0. Loopstra, J . Inorg. Nucl. Chem., 33, 2427 (1971). 2. A. F. Wells, Structural Inorganic Chemistry, Clarendon Press, Oxford, 1975, p. 1003.
3.10.3.5 Mixed Valence, Mixed Anion Phases, Including Oxides with Cations of Variable Valence (or Mixed Cations) Balanced by Substitution of Altervalent Anions Nonstoichiometric compositions in oxide phases can occur by substitution of monovalent anions, typically halide or hydroxide, for oxide anions. One class of such oxyhalides involves replacement of oxide ions by twice the number of halide ions, so that no formal metal cation valence change occurs. Many group IIIA element examples occur. The yttrium oxyfluoride system is a particularly well-characterized example (see 3.10.3.5.1).A second class of mixed anion nonstoichiometric oxides involves one-for-one replacement of oxide anions by monovalent anions, resulting in a decrease in the formal positive valence of a corresponding number of cations. Oxyfluoride phases with the ReO, structure of the type M 0 3 -,F, illustrate this class of nonstoichiometry' - 4 . Substitution of the monovalent halide anion for the divalent oxide anion introduces another electron into the band structure of the solid. In the cases of MO and W oxide systems M o o 3-xFx and WO,-,F,, the extra electron goes into a conduction band so that the phases are metallic conductors with ranges of colors and luster. The similarities to the M O and W bronzes, for which these compounds are the exact electronic analogues, is striking. Among the N b and Ta oxyfluorides, the compositions M 0 3-,F, vary in values of x from 1 to nearly 3 in a continuous series3. All phases exist in the R e 0 3 structure, wherein the metal atom is in octahedral coordination with six 0 atoms. In the ideal R e 0 3 structure, the oxygens lie at the midpoint of the line connecting adjacent Re atoms, but the structure will accommodate distortions from that symmetry. The oxyfluorides are prepared5 by heating the metal trioxides, the metal, and H F in sealed gold capsules at 700°C and 3 kbar for 8 h. Under these conditions, Mo03-,F, compositions form with a maximum value of x = 0.66. Compositions with 0.74 < x < 0.97 had the cubic R e 0 3 structure. The W 0 3-,F, system ranged to a maximum value of x = 0.66 with the cubic R e 0 3 structure occurring in the range 0.17 < x < 0.66. (L. E. CONROY)
1. D. Bable, in Structure and Bonding, Vol. 111, C. K. Jorgensen, ed., Springer-Verlag, New York,
1967, p. 31. 2. K. Vorres, J. Donohue, Acta Crystallogr., 8, 25 (1955). 3. H. Schafer, H. G. Schnering, K. J. Niehues, H. G. Nieder-Vaharenholz, J . Less-Common Met., 9, 95 (1965). 4. D. E. LaValle, R. M. Steele, M. K. Wilkinson, H. L. Yakel, J . Am. Chem. Soc., 82, 2433 (1960). 5. A. W. Sleight, Inorg. Chem., 8, 1964 (1969).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.11 Formation of the Nonstoichiometric Sulfides,
Selenides, and Tellurides 3.1 1.1 Introduction These compounds show unique chemical, crystallographic, and physical properties that attract the interest of solid state scientists. Modern spectroscopic, magnetic, and structural investigations coupled with theoretical calculations reveal the electronic interactions between metal and chalcogen leading to a wealth of properties of the chalcogenides with d 1 - 6 andf-metal~’-~. As the ionic character of the bonding decreases with increasing atomic number of the chalcogen, nonstoichiometry and metallicity are more pronounced in the selenides and tellurides. However, for reasons discussed in 3.11.2, there are also many metallic sulfides. Ionic chalcogenides are formed only with the group IA metals. Already the group IIA metals form covalent chalcogenides. The metallic and semimetallic chalcogenides of the transition metal series show large homogeneity ranges. Therefore, thermodynamically, they must be treated as alloy phases (solid solutions), rather than stoichiometric compounds. As shown in the 3.11.2,chemical control of nonstoichiometry enables physical properties to be varied. As variation of the physical and structural properties is the most sensitive probe of chemical bonding changes, control of chemical composition (and structure) based on exact knowledge of the P - 7 - x phase diagram becomes of primary importance to the solid state chemistry. On the other hand, with increasingly high mp, tendency to decomposition, and chemical reactivity, the investigation of the phase relationships and thermodynamic properties of these compounds becomes difficult at temperatures higher than 1100‘C (thermal stability limit of quartz glass ampules). To achieve crystal growth in the rare earth chalcogenides (mp > 2000’C), the foregoing difficulties can be overcome by use of evacuated W crucibles sealed by electron and by applying differential thermal analysis to investigate the phase diagrams up to 2400’C’2, 1 3 . For the &transition metal chalcogenides, compatibility problems exist for W; therefore, other metals must be used. For several of these compounds, however, at least crystal growth, a necessary condition for serious solid state investigations, is possible by chemical transport or s ~ b l i m a t i o n”.~ ~ , (E. KALDIS)
1. F. Jellinek, M T P Int. Rec. Sci., Inorg. Chem. Ser., 5,339 (1972).Recommended reading. A review of the crystal chemical properties of the chalcogenides. 2. E. Kaldis, ed., Current Topics in Materials Science, Vol. 3, North-Holland, Amsterdam, 1979. 3. C. Haas, M T P Int. Rev. Sci., Inorg. Chem. Ser., 3, 1 (1979). Theoretical aspects are stressed. 4. C. F. van Bruggen, Ann. Chim. Fr., 7; 171 (1982). Short but clear review. 5. A. Meerschaut, Ann. Chim. Fr. 7, 131 (1982). Lecture notes. 6. J. Rouxel, Phjsica, 99B, 3 (1980). 7. P. Wachter, in Handbook on the Physics and Chemistry of the Rare Earths, K. A. Gschneider, L. Eyring, eds., Vol. 2, 1979, p. 507. North-Holland, Amsterdam, Recommended reading.
25 1
252
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.2 Chemical Bonding and Variation of Physical Properties 3.1 1.2.1 &Transition Metal Chalcogenides
8. J. M. Lawrence, P. S. Riseborough, R. D. Parks, Rep. Prog. Phys., 44, 1 (1981). The latest progress report on mixed valence. 9. E. Kaldis, B. Fritzler, H. Spychiger, in European Solid State Chemistry Conference, 1982, R. Metselaar, ed., Elsevier, Amsterdam, 1982, p. 89. A short introduction for chemists to the valence fluctuation phenomena. Recommended reading. 10. E. Kaldis, J . Cryst. Growth, 9, 281 (1971); 24/25, 53 (1974). 11. E. Kaldis, in Crystal Growth, Theory and Techniques, C. H. L. Goodman, ed., Vol. I, Plenum Press, 1974, New York, p. 49. 12. E. Kaldis, W. Peteler, in Thermal Analysis, Proceedings of the 6th International Conferences Bayreuth, Germany, Birkhauser Verlag, Basel, 1980, p. 67. 13. E. Kaldis, B. Fritzler, in Prog. Solid State Chem. 14, 95 (1982). 14. E. Wolf, H. Opperman, G. Krabbes, W. Reichelt, Ref. 2, Vol. 1, 697 (1978). Review of chemical transport methods for crystal growth of nonstoichiometric FeS,. Recommended reading. 15. F. Levy, H. Berger, J . Cryst. Growth, (1982). Introduction to the crystal growth literature for d-transition metal tri- and dichalcogenides.
3.11.2 Chemical Bonding and Variation of Physical Properties by Means of Chemical Parameters 3.1 1.2.1 &Transition Metal Chalcogenides
Interaction of the outer s- and p-metal orbitals of the d metals with the orbitals of the chalcogen leads to formation of bonding (valence band) and antibonding (conduction band) states, both in the chalcogenides of the main group and in the transition metals. In
-3
-
iu
w
T / Y
-
roo
140
Figure 1. Influence of controlled nonstoichiometry on the metal-semiconductor phase transition of FeS,. Logarithm of the electrical resistivity as a function of T s .
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
252
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.2 Chemical Bonding and Variation of Physical Properties 3.1 1.2.1 &Transition Metal Chalcogenides
8. J. M. Lawrence, P. S. Riseborough, R. D. Parks, Rep. Prog. Phys., 44, 1 (1981). The latest progress report on mixed valence. 9. E. Kaldis, B. Fritzler, H. Spychiger, in European Solid State Chemistry Conference, 1982, R. Metselaar, ed., Elsevier, Amsterdam, 1982, p. 89. A short introduction for chemists to the valence fluctuation phenomena. Recommended reading. 10. E. Kaldis, J . Cryst. Growth, 9, 281 (1971); 24/25, 53 (1974). 11. E. Kaldis, in Crystal Growth, Theory and Techniques, C. H. L. Goodman, ed., Vol. I, Plenum Press, 1974, New York, p. 49. 12. E. Kaldis, W. Peteler, in Thermal Analysis, Proceedings of the 6th International Conferences Bayreuth, Germany, Birkhauser Verlag, Basel, 1980, p. 67. 13. E. Kaldis, B. Fritzler, in Prog. Solid State Chem. 14, 95 (1982). 14. E. Wolf, H. Opperman, G. Krabbes, W. Reichelt, Ref. 2, Vol. 1, 697 (1978). Review of chemical transport methods for crystal growth of nonstoichiometric FeS,. Recommended reading. 15. F. Levy, H. Berger, J . Cryst. Growth, (1982). Introduction to the crystal growth literature for d-transition metal tri- and dichalcogenides.
3.11.2 Chemical Bonding and Variation of Physical Properties by Means of Chemical Parameters 3.1 1.2.1 &Transition Metal Chalcogenides
Interaction of the outer s- and p-metal orbitals of the d metals with the orbitals of the chalcogen leads to formation of bonding (valence band) and antibonding (conduction band) states, both in the chalcogenides of the main group and in the transition metals. In
-3
-
iu
w
T / Y
-
roo
140
Figure 1. Influence of controlled nonstoichiometry on the metal-semiconductor phase transition of FeS,. Logarithm of the electrical resistivity as a function of T s .
3.11 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 253 3.1 1.2 Chemical Bonding and Variation of Physical Properties 3.1 1.2.2 4f-Transition Metal (Rare Earth) Chalcogenides
d-transition metals an additional weaker, but important interaction of the d orbitals with the p orbitals of the chalcogen appears, which is responsible for the characteristic properties of the transition metal chalcogenides. Compared to the p and s orbitals, the d orbitals of the metal ion have small spatial extension. Therefore, small d / p overlap (covalency) leads to localized (atomlike) d states in the crystal’,’. With increasing d / p overlap, the d states develop to narrow d bands. The energies of the lowest empty and the highest occupied d bands relative to the valence (chalcogen) and conductivity (metal) bands decide the conduction character (semiconductor, semimetal, meta1)3,4.Owing to the low spatial extension of the d orbitals, the degree of d / p overlap depends critically on parameters such as electron configuration of the transition metal (including valence state), interatomic distance, coordination number, and of course the relation of the two energy term diagrams, (i.e., the energy separation between the interacting d states of the transition metal and the p states of the ~halcogen)~. Mixed crystal formation and nonstoichiometry can be used to vary the physical properties of these compounds (see 3.1 1.2.2). These tools change interatomic distances and the carrier concentration, which may influence the degree of localization of the d bands, the crystal field splitting, the magnetic exchange interaction, etc. A classic example of changing the physical properties by controlling the nonstoichiometry during crystal growth is shown in Figure 1’. Hysteresis and temperature of the metal-semiconductor phase transition in FeS, change as a function of nonstoichiometry. (E. KALDIS) 1. F. Jellinek, M T P Int. Rev. Sci. Inorg. Chem. Ser., 5, 339 (1972). Recommended reading. A complete review of the crystal chemical properties of the chalcogenides. 2. E. Kaldis, ed., Current Topics in Materials Science, Vol. 3, North-Holland, Amsterdam, 1979. 3. C. Haas, M T P Int. Rev. Sci. Inorg. Chem. Ser., 3, 1 (1979). Theoretical aspects are stressed. 4. C. F. van Bruggen, Ann. Chim. Fr., 7, 171 (1982). Short but clear review with recent results and introduction to the literature. 5. E. Wolf, H. Opperman, G. Kuabbes, W. Reichelt, Ref. 2, Vol. 1, 697 (1978). Review of chemical transport methods for crystal growth of nonstoichiometric FeS,.
3.11.2.2 4f-Transition Metal (Rare Earth) Chalcogenides
In these compounds the 4f level is localized; in the divalent, semiconducting rare earth monochalcogenides (NaC1 structure), the 4f level lies between the occupied ( p ) valence band of the chalcogen ions and the empty ( 5 4 conduction band of the rare earth ions. The promotion of the 4f” electrons is more energetically favored than that of electrons in the valence band. For the semiconducting, ferromagnetic Eu chalcogenides, the 4felectrons are both carriers of magnetism and conduction electrons (ferromagnetic semiconductors)’. In the trivalent rare earth monochalcogenides the 5d band is not empty and the 4 p - I level overlaps with the valence band or lies lower, up to 10 eV from the Fermi level (electrostatic correlation energy)’. The energy separation between the localized 4flevel and the bottom of the 5d band in the divalent chalcogenides varies between 2.0 eV for EuTe and < 0.1 eV for Sic. This band gap is so narrow that it can be closed by applying pressure (6.5 kbar)’ due to the following mechanism. The 5d band of the rare earth monochalcogenides is split, owing to the crystal field, to the e, and t z g subbands. The pressure decreases the interatomic distance and, therefore, increases the crystal field splitting. In this way the t z s subband approaches the 4f level. When the gap becomes very small, there is an isostructural
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.11 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 253 3.1 1.2 Chemical Bonding and Variation of Physical Properties 3.1 1.2.2 4f-Transition Metal (Rare Earth) Chalcogenides
d-transition metals an additional weaker, but important interaction of the d orbitals with the p orbitals of the chalcogen appears, which is responsible for the characteristic properties of the transition metal chalcogenides. Compared to the p and s orbitals, the d orbitals of the metal ion have small spatial extension. Therefore, small d / p overlap (covalency) leads to localized (atomlike) d states in the crystal’,’. With increasing d / p overlap, the d states develop to narrow d bands. The energies of the lowest empty and the highest occupied d bands relative to the valence (chalcogen) and conductivity (metal) bands decide the conduction character (semiconductor, semimetal, meta1)3,4.Owing to the low spatial extension of the d orbitals, the degree of d / p overlap depends critically on parameters such as electron configuration of the transition metal (including valence state), interatomic distance, coordination number, and of course the relation of the two energy term diagrams, (i.e., the energy separation between the interacting d states of the transition metal and the p states of the ~halcogen)~. Mixed crystal formation and nonstoichiometry can be used to vary the physical properties of these compounds (see 3.1 1.2.2). These tools change interatomic distances and the carrier concentration, which may influence the degree of localization of the d bands, the crystal field splitting, the magnetic exchange interaction, etc. A classic example of changing the physical properties by controlling the nonstoichiometry during crystal growth is shown in Figure 1’. Hysteresis and temperature of the metal-semiconductor phase transition in FeS, change as a function of nonstoichiometry. (E. KALDIS) 1. F. Jellinek, M T P Int. Rev. Sci. Inorg. Chem. Ser., 5, 339 (1972). Recommended reading. A complete review of the crystal chemical properties of the chalcogenides. 2. E. Kaldis, ed., Current Topics in Materials Science, Vol. 3, North-Holland, Amsterdam, 1979. 3. C. Haas, M T P Int. Rev. Sci. Inorg. Chem. Ser., 3, 1 (1979). Theoretical aspects are stressed. 4. C. F. van Bruggen, Ann. Chim. Fr., 7, 171 (1982). Short but clear review with recent results and introduction to the literature. 5. E. Wolf, H. Opperman, G. Kuabbes, W. Reichelt, Ref. 2, Vol. 1, 697 (1978). Review of chemical transport methods for crystal growth of nonstoichiometric FeS,.
3.11.2.2 4f-Transition Metal (Rare Earth) Chalcogenides
In these compounds the 4f level is localized; in the divalent, semiconducting rare earth monochalcogenides (NaC1 structure), the 4f level lies between the occupied ( p ) valence band of the chalcogen ions and the empty ( 5 4 conduction band of the rare earth ions. The promotion of the 4f” electrons is more energetically favored than that of electrons in the valence band. For the semiconducting, ferromagnetic Eu chalcogenides, the 4felectrons are both carriers of magnetism and conduction electrons (ferromagnetic semiconductors)’. In the trivalent rare earth monochalcogenides the 5d band is not empty and the 4 p - I level overlaps with the valence band or lies lower, up to 10 eV from the Fermi level (electrostatic correlation energy)’. The energy separation between the localized 4flevel and the bottom of the 5d band in the divalent chalcogenides varies between 2.0 eV for EuTe and < 0.1 eV for Sic. This band gap is so narrow that it can be closed by applying pressure (6.5 kbar)’ due to the following mechanism. The 5d band of the rare earth monochalcogenides is split, owing to the crystal field, to the e, and t z g subbands. The pressure decreases the interatomic distance and, therefore, increases the crystal field splitting. In this way the t z s subband approaches the 4f level. When the gap becomes very small, there is an isostructural
254
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.2 Chemical Bonding and Variation of Physical Properties 3.1 1.2.2 4f-Transition Metal (Rare Earth) Chalcogenides
(NaCI), pressure-induced, semiconductor-to-metal transition, with an increase of oxidation state from Sm2+(4f65d06s2)to Sm3+(4f55d16s2)3.The 4felectron is not permanently promoted to the 5d band, but it fluctuates between the localized (4f) and delocalized ( 5 4 state with a frequency of 109-1015 H z ~(valence , ~ fluctuation). As the occupation number of the 4f states becomes non integral, the valence of the cation becomes nonintegral or mixed3 Variation of nonstoichiometry in such compounds (e.g., TmSe) results in a controlled change of the valence between Tm3" and Tm2 7 5 + '. Lattice parameters5; and thermodynamic5 and physical properties6 change dramatically as a function of valence. Thus, the resistivity at T < 10 K increases by many orders of magnitude with only small changes in the nonstoichiometry. Figure 1 shows the change of the lattice parameter of TmSe as a function of nonstoichiometry. The large change of Aala 1.7% is due to the change of valence ( 3.0+2.75), which can be estimated by an interpolation of the lattice constants of the rare earth selenides?. Precision density measurements lead to a model for the defect structure. Larger changes of the Tm valence coupled with a composition induced, isostructural metal-to-semiconductor phase transition, are reached by alloying TmSe with the larger ions Te2- or EuZC(TmSe1-,Te,, Tml -.Eu,Se). In this way the Tm-Tm distance is increased with increasing concentration. The crystal field
-
+
jl/l 5768
,,,,,,,
[ 51
-5980 -578
Figure 1. Change of valence of Tm in TmSe as shown by change of the lattice constant (NaCl structure) as a function of nonstoichiometry. The width of the homogeneity range of the mixed valence state 0.98 < Tm/Se < 1.05 is also shown. A miscibility gap 0.94 < Tm,iSe < 0.98 is separating the Tm3+Sephase from the mixed valence state (After Ref. 5.).
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 255 3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic splitting decreases as well, and a gap is opened in the band structure of TmSe (between 5d and 4f)7. (E. KALDIS) 1. P. Wachter, in Handbook on the Physics and Chemistry of the Rare Earths, Vol. 2, K. A. Gschneider, L. Eyring, eds., 1979, p. 507. North-Holland, Amsterdam, Recommended reading. 2. A. Jayaraman, in Handbook of the Physics and Chemistry of Rare Earths, Vol. 2, K. A. Gschneidner, L. Eyring, eds., North-Holland, Amsterdam, 1979, p. 575. 3. J. M. Lawrence, P. S. Riseborough, R. D. Parks, Rep. Prog. Phys. 44, 1 (1981). 4. E. Kaldis, B. Fritzler, H. Spychiger, in Proceedings of the 2nd European Solid State Chemistry Conference 1982, R. Metselaar, ed., Elsevier, Amsterdam, 1982. A short introduction for chemists to the valence fluctuation phenomena. Recommended reading. 5. E. Kaldis, B. Fritzler, in Prog. Solid State Chem., 14, 95 (1982). 6. B. Batlogg, H. R. Ott, E. Kaldis, W. Thoni, P. Wachter, Phys. Rev. B, 19, 247 (1979). 7. E. Kaldis, B. Fritzler, J . Phys. (Paris), 11, C5 (1980).
3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic Parameters The synthesis of pure and homogeneous solid phases with reproducible properties is difficult. The reproducibility of properties, which depends on the reproducibility of defect structure, is best achieved by growth of single crystals under specified thermodynamic conditions (e.g., partial pressure of the chalcogen, temperature, etc.). Thus syntheses from the pure elements are more meaningfully presented when based on thermodynamic criteria. Most metals react directly with S, Se, and Te to form binary compounds. Synthesis from these elements can be used for most ternary chalcogenides as well as mixed crystals of isostructural binary chalcogenides. The metal should be in form of turnings or pieces instead of powder, which is always contaminated with impurities. The turnings must be prepared in inert atmosphere (for reactive metals the concentration of 0 2 and the humidity should be less than 3 ppm atm), immediately before use. For strongly exothermal sulfides (e.g., EuS), the metal may burn in the sulfur atmosphere causing the reaction to go out of control (sudden evaporation of sulfur; explosion of the ampule). For this reason, it is necessary to separate the two reactants by using a two-chamber quartz T o avoid reaction with the quartz walls, temperature should not exceed 8 5 0 T . Depending on the phase diagram and the kinetics of phase formation other phases may be initially formed, e.g., with the rare earth chalcogenides, particularly the heavy chalcogenides. Owing to the large ionic radius both of metal and non-metal, the diffusion processes is rate determining at T < 1200'C. In the first stage, a surface reaction takes place with an abundance of the chalcogen. This leads to formation of chalcogen-rich phases at the outer part of the metal and chalcogen-poor phases at the core of the metal turnings. No attempt should be made to increase homogeneity by means of the traditional grinding and reheating of this reaction product, a process that increases contamination. Where crystal growth with chemical transport is planned, and doping with the transporting agent is harmless, easy homogenization of the reaction product is possible. The transporting agent is sealed in the ampule together with the elements and heated in a gradient. The chalcogenide formed on the metal surface is continuously transported.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 255 3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic splitting decreases as well, and a gap is opened in the band structure of TmSe (between 5d and 4f)7. (E. KALDIS) 1. P. Wachter, in Handbook on the Physics and Chemistry of the Rare Earths, Vol. 2, K. A. Gschneider, L. Eyring, eds., 1979, p. 507. North-Holland, Amsterdam, Recommended reading. 2. A. Jayaraman, in Handbook of the Physics and Chemistry of Rare Earths, Vol. 2, K. A. Gschneidner, L. Eyring, eds., North-Holland, Amsterdam, 1979, p. 575. 3. J. M. Lawrence, P. S. Riseborough, R. D. Parks, Rep. Prog. Phys. 44, 1 (1981). 4. E. Kaldis, B. Fritzler, H. Spychiger, in Proceedings of the 2nd European Solid State Chemistry Conference 1982, R. Metselaar, ed., Elsevier, Amsterdam, 1982. A short introduction for chemists to the valence fluctuation phenomena. Recommended reading. 5. E. Kaldis, B. Fritzler, in Prog. Solid State Chem., 14, 95 (1982). 6. B. Batlogg, H. R. Ott, E. Kaldis, W. Thoni, P. Wachter, Phys. Rev. B, 19, 247 (1979). 7. E. Kaldis, B. Fritzler, J . Phys. (Paris), 11, C5 (1980).
3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic Parameters The synthesis of pure and homogeneous solid phases with reproducible properties is difficult. The reproducibility of properties, which depends on the reproducibility of defect structure, is best achieved by growth of single crystals under specified thermodynamic conditions (e.g., partial pressure of the chalcogen, temperature, etc.). Thus syntheses from the pure elements are more meaningfully presented when based on thermodynamic criteria. Most metals react directly with S, Se, and Te to form binary compounds. Synthesis from these elements can be used for most ternary chalcogenides as well as mixed crystals of isostructural binary chalcogenides. The metal should be in form of turnings or pieces instead of powder, which is always contaminated with impurities. The turnings must be prepared in inert atmosphere (for reactive metals the concentration of 0 2 and the humidity should be less than 3 ppm atm), immediately before use. For strongly exothermal sulfides (e.g., EuS), the metal may burn in the sulfur atmosphere causing the reaction to go out of control (sudden evaporation of sulfur; explosion of the ampule). For this reason, it is necessary to separate the two reactants by using a two-chamber quartz T o avoid reaction with the quartz walls, temperature should not exceed 8 5 0 T . Depending on the phase diagram and the kinetics of phase formation other phases may be initially formed, e.g., with the rare earth chalcogenides, particularly the heavy chalcogenides. Owing to the large ionic radius both of metal and non-metal, the diffusion processes is rate determining at T < 1200'C. In the first stage, a surface reaction takes place with an abundance of the chalcogen. This leads to formation of chalcogen-rich phases at the outer part of the metal and chalcogen-poor phases at the core of the metal turnings. No attempt should be made to increase homogeneity by means of the traditional grinding and reheating of this reaction product, a process that increases contamination. Where crystal growth with chemical transport is planned, and doping with the transporting agent is harmless, easy homogenization of the reaction product is possible. The transporting agent is sealed in the ampule together with the elements and heated in a gradient. The chalcogenide formed on the metal surface is continuously transported.
256
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic 3.1 1.3.1 Control of Nonstoichiometty
Transporting the material to opposite sides of the tube several times results in excellent homogeneity. If no transporting agent can be used, best homogenization is achieved by heating at high temperatures in evacuated sealed metal crucibles’s’. The solid is then in equilibrium with the vapor phase of the compound. Kinetic effects of surface layers on metals can lead to formation of other phases. When Tm turnings react with Te vapor, Tm3+Te(NaC1 structure) with a lattice constant a = 6.038 forms together with a rhombohedra1 phase. Single crystals grown from the melt have also the NaCl structure, but the lattice constant, a = 6.350 corresponds to the semiconductor Tm2+Te.In view of the changes of the valence of Tm in TmSe as a function of nonstoichiometry (see Fig. 1, 3.11.2.2), it is possible that in TmTe also a composition- and temperature-induced transition from metal to semiconductor phase takes place. The surface reactions on an atomic scale of transition metals with sulfur give examples of early stages of epitaxy3. The temperatures of the two reactants must be separately controlled via a two-zone furnace to control the velocity of the product formation. However, the main reason for independent regulation of temperature is the need to control stoichiometry of the product via the partial pressure of one component (see 3.11.3.1). To avoid inhomogeneities of the product owing to kinetic diffusion problems at lower temperatures, the solid can be precipitated from the reaction of the vapors of the elements. The method is applicable only for volatile metals, e.g., CdS4. The vapors are carried to a reaction chamber by inert gas flow. Use of reacting gases like H2S5 combines chemical transport with the method above.
a
a,
(E. KALDIS) 1. E. Kaldis, in J . Cryst. Growth, 9 , 281 (1971); 24/25, 53 (1974). 2. E. Kaldis, in Crystal Growth, Theory and Techniques, Vol. I, C. H. L. Goodman, ed., Plenum Press, New York, 1974, p. 49. 3. R. Kern, G. Le Lay, J. J. Metois, in “Current Topics in Materials Science”, E. Kaldis, ed., Vol. 3, 139 (1979), North Holland, Amsterdam, 1979. 4. See, e.g., K. Nassau, J. W. Shiever, J . Cryst. Growth, 13/14, 375 (1972). 5. P. Flogel, Krist. Tech., 3 , 161 (1968); 6, 499 (1971).
3.1 1.3.1 Control of Nonstoichiometry
Figure 1 shows the P-x section of the P-T-x phase diagram of the binary system A-B (A = chalcogen, B = metal) in which only the nonstoichiometric 1 : 1 compound (AB)sis formed. For simplicity, the shape of the homogeneity range is symmetrical to the stoichiometric 1 : 1 composition. In reality, however, asymmetrical homogeneity ranges also exist. The compound (AB)s coexists with the vapor phase in a wide range: P ( r (AB),). However, depending on P , compositions of the solid compound and the vapor are different. Thus at P’ the vapor and solid compositions in equilibrium are 0‘ and s‘, and at P” we have L“’ and s“, respectively. The minimum pressure at which solid and vapor can coexist is PI”. At this pressure the solid and vapor have the same composition, which lies near the stoichiometric one. Depending on the enthalpy of formation of vacancies of the anion and the cation, the minimum value of P lies slightly offstoichiometry on the chalcogen- or metal-rich side. The existence of a pressure minimum (Pmin = P”’) implies that evaporation in vacuum will adjust stoichiometry (strictly speaking, the solid composition corresponding to P,,,). As the A-rich vapor of the
+
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
256
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic 3.1 1.3.1 Control of Nonstoichiometty
Transporting the material to opposite sides of the tube several times results in excellent homogeneity. If no transporting agent can be used, best homogenization is achieved by heating at high temperatures in evacuated sealed metal crucibles’s’. The solid is then in equilibrium with the vapor phase of the compound. Kinetic effects of surface layers on metals can lead to formation of other phases. When Tm turnings react with Te vapor, Tm3+Te(NaC1 structure) with a lattice constant a = 6.038 forms together with a rhombohedra1 phase. Single crystals grown from the melt have also the NaCl structure, but the lattice constant, a = 6.350 corresponds to the semiconductor Tm2+Te.In view of the changes of the valence of Tm in TmSe as a function of nonstoichiometry (see Fig. 1, 3.11.2.2), it is possible that in TmTe also a composition- and temperature-induced transition from metal to semiconductor phase takes place. The surface reactions on an atomic scale of transition metals with sulfur give examples of early stages of epitaxy3. The temperatures of the two reactants must be separately controlled via a two-zone furnace to control the velocity of the product formation. However, the main reason for independent regulation of temperature is the need to control stoichiometry of the product via the partial pressure of one component (see 3.11.3.1). To avoid inhomogeneities of the product owing to kinetic diffusion problems at lower temperatures, the solid can be precipitated from the reaction of the vapors of the elements. The method is applicable only for volatile metals, e.g., CdS4. The vapors are carried to a reaction chamber by inert gas flow. Use of reacting gases like H2S5 combines chemical transport with the method above.
a
a,
(E. KALDIS) 1. E. Kaldis, in J . Cryst. Growth, 9 , 281 (1971); 24/25, 53 (1974). 2. E. Kaldis, in Crystal Growth, Theory and Techniques, Vol. I, C. H. L. Goodman, ed., Plenum Press, New York, 1974, p. 49. 3. R. Kern, G. Le Lay, J. J. Metois, in “Current Topics in Materials Science”, E. Kaldis, ed., Vol. 3, 139 (1979), North Holland, Amsterdam, 1979. 4. See, e.g., K. Nassau, J. W. Shiever, J . Cryst. Growth, 13/14, 375 (1972). 5. P. Flogel, Krist. Tech., 3 , 161 (1968); 6, 499 (1971).
3.1 1.3.1 Control of Nonstoichiometry
Figure 1 shows the P-x section of the P-T-x phase diagram of the binary system A-B (A = chalcogen, B = metal) in which only the nonstoichiometric 1 : 1 compound (AB)sis formed. For simplicity, the shape of the homogeneity range is symmetrical to the stoichiometric 1 : 1 composition. In reality, however, asymmetrical homogeneity ranges also exist. The compound (AB)s coexists with the vapor phase in a wide range: P ( r (AB),). However, depending on P , compositions of the solid compound and the vapor are different. Thus at P’ the vapor and solid compositions in equilibrium are 0‘ and s‘, and at P” we have L“’ and s“, respectively. The minimum pressure at which solid and vapor can coexist is PI”. At this pressure the solid and vapor have the same composition, which lies near the stoichiometric one. Depending on the enthalpy of formation of vacancies of the anion and the cation, the minimum value of P lies slightly offstoichiometry on the chalcogen- or metal-rich side. The existence of a pressure minimum (Pmin = P”’) implies that evaporation in vacuum will adjust stoichiometry (strictly speaking, the solid composition corresponding to P,,,). As the A-rich vapor of the
+
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 257 3.11.3 Synthesis and Crystal Growth Under Controlled Thermodynamic 3.1 1.3.1 Control of Nonstoichiometry
t
P
P'
P"
,Pi,
= P"'
A
V'
V"
S' 9 A B
B
XFigure 1. Phase diagram of a binary system (A = chalcogen, B = metal) showing pressure P versus x at a temperature where the compound experiences a minimum of the vapor pressure. For details see text. compound is removed, the vapor pressure decreases (P' + P"') and composition nears stoichiometry. Therefore, the phase diagram gives the dependence of the nonstoichiometry on the chalcogen partial P . If things are so simple, why has control of nonstoichiometry of most compounds not yet been achieved? The difficulties arise either by the determination of x (Fig. 1) or by the lack of Pmin.For compounds with narrow nonstoichiometric ranges (e.g., the group 11-VI compounds), it is difficult to determine x with the necessary accuracy. Knowledge of the defect structure, however, leads to a calibration of nonstoichiometry versus a physical property that can be measured more accurately than chemical composition, e.g., in the exact control of nonstoichiometry in PbS' and other chalcogenides' to vary their electrical properties. The Pminappears only up to the temperature of the maximum sublimation point'. At higher temperatures the compound decomposes (loss of chalcogen) to form B-rich liquid and vapor. Depending on the thermodynamic stability of the compound, the temperature of the maximum sublimation point may become low.
258
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 3.11.3 Synthesis and Crystal Growth Under Controlled Thermodynamic 3.1 1.3.1 Control of Nonstoichiometry
Increase of the chalcogen pressure in the range up to 50 atm, which can be achieved by thick-walled ampules (take measures against explosion!),will lead to a suppression of decomposition of most chalcogenides in the range of the thermal stability of the quartz glass ampules ( T < 1100°C). The increase of pressure may also induce other effects: stabilization of molecules of the compound in the vapor (possibility of undissociative sublimation), formation of polymeric vapor molecules of the (AB), type, or polyanionic molecules of the AB, type. Both can lead to endothermic chemical transport via entropy stabilization3. It can be estimated that much larger pressures4 of the chalcogen ( P > 5-7 kbar) may change the defect structure by introducing interstitials that could be quenching at RT and atmospheric pressure. Since this would change the electric properties, p-n junctions from the same group 11-VI compounds could be envisaged, and a longstanding dream of materials science could be realized. For the synthesis of chalcogenides of a given nonstoichiometric composition, the following experimental conditions can apply:
1. If the homogeneity range is wide ( > 1 atom YO), the nonstoichiometry of the product can be varied by sealing appropriate amounts of the elements in the ampule. Chemical analysis can be used to check the composition of the chalcogenide product. Only the analysis of the metal can be used, which in the best case (e.g. complexometric titration) reaches an accuracy of ca. & 0.2 atom YO.This is comparable to results of the adjustment of the nonstoichiometry with exactly known amounts of elements. The accuracy of the determination of the chalcogen by chemical analysis is ca. 0.5-0.8 atom %. 2. The nonstoichiometry of crystals grown at higher temperatures can be adjusted by annealing them in a bed of powder of the wanted stoichiometry, sealed in an ampule and heated at a temperature that will permit the achievement of thermodynamic equilibrium. 3. Annealing in the appropriate partial pressure of the volatile component. This is combined with crystal growth by sublimation, e.g., for PbSes or ZnSe6. 4. For a final composition near the exact stoichiometry, where the compound has at convenient temperatures a pressure minimum (see above). Heating in vacuum will reduce the excess component and adjust stoichiometry. However, for single-crystal growth in a sealed ampule, an open capillary or a hole of ca. 0.2 mm diameter can be used. At the usual sublimation pressures of pta < 10 torr, reduced pressure outside the ampule induces molecular flow of the evaporating species through the hole. At the steady state the vapor components effuse at the ratio of their molecular weights, PM,/PX2 = MMe/Mxl(condition of congruent evaporation). In this way the stoichiometry of the sublimate is adjusted to a fixed value, e g , for ZnTe7 and CdS8. The stoichiometry can be changed by introducing a partial pressure of one of the components in the atmosphere around the ampule. Such methods do not have any advantages compared with condition 3. A classical method to fix small partial pressures of sulfur above sulfides is the buffered H,S/H, atmosphere where theoretically Ps, as small as lo-'' atm can be appliedg.Attention should be paid, however, to the influence of H2 on the properties of the solid. (E. KALDIS)
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 259 3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic 3.1 1.3.2 Chemical Vapor Transport of the Chalcogenides 1. J. Bloem, F. A. Kroger, Z . Phys. Chem., 7, l(1956). 2. F. A. Kroger, T h e Chemistry oflmperfect Crystals, Vol. I, North-Holland, Amsterdam, 1973. The best textbook in the field. Recommanded reading. 3. E. Kaldis, J . Cryst. Growth, 24/25, 53 (1974). 4. For high pressure synthesis see S. Porowski, J . Cryst. Growth, 166, 583 (1996) and therein mentioned literature. 5. A. C. Prior, J . Electrochem. Soc., 108, 82 (1961). 6. K. Igaki, S. Satoh, Jpn. J . Appl. Phys., 18, 1965 (1979); Trans. Jpn. Inst. Met., 13, 248 (1972). 7. T. Vamanaka, T. Shiraishi, Jpn. J . Appl. Phys., 4, 826 (1956). 8. M. M. Faktor, I. Garrett, Growth of Crystalsfrom the Vapor, Chapman & Hall, London, 1974. 9. R. A. Swalin, Thermodynamics of Solids, Wiley, New York, 1966.
3.11.3.2 Chemical Vapor Transport of the Chalcogenides Synthesis and crystal growth of chalcogenides (and many other compounds, e.g.; oxides) may also take place by chemical transport'. Such reactions lead to chemical mass transport if a solid can reversibly react with a gaseous reactant to yield a gaseous product, e.g.: ZnSe(s)
+ 12(g)+ Zn12(g)+ Se T2
T,
Cd4GeS6(s)
+ 512(g)+ 4Cd12 + Ge12 + 3S2
(b)
Upon application of a temperature gradient (AT = T 2 - TI),the chemical equilibrium is shifted so that chemical evaporation of the source takes place at T 2 and precipitation of the solid from the vapor phase at T1. Apart from unintentional doping with the transporting agent, which in some cases (e.g., group IIB-VIB compounds) influences the physical properties, chemical transport can be advantageous for preparative solid state chemistry: 1. Contrary to the direct reaction from the elements (see 3.1 1.3: solid vapor reaction), no
diffusional constraints appear in the presence of a chemical transporting agent. Thus if the thermodynamics of the reaction are known, homogeneous phases can be prepared. 2. Chemical evaporation takes place at appreciably lower temperatures than those of the corresponding sublimation. Thus crystals can be grown at lower temperatures (e.g., CdS and ZnSe melt at 1475 and 1520'C, respectively, and their corresponding decomposition pressures at mp are 3.8 and 0.53 atm). Crystals are grown by sublimation at ca. 1100°C. For chemical transport with 12, T 750°C is s ~ f f i c i e n t ~ . ~ .
-
Simple thermodynamic rules for chemical transport reactions are formulated'. The thermodynamic driving force of chemical transport is the shift of the chemical equilibrium (free energy of the reaction, AG = AGT2- AGT,) along the temperature gradient. In view of the reverse reaction, extreme values of the equilibrium constant are not suitable. Values of K r , / K T , = K z 1 (AG = - RT In K , N 0) are ideal. The transport takes place from high concentration of the volatile product (more negative AGT,) to lower concentration (less negative AGT,).For most reactions this appears when T I exceeds T 2 ,i.e., when the solid is migrating from hot to cold (endothermal transport; increasing vapor pressure of the volatile product with increasing T ) .For exothermic volatile products (i.e., decomposing at higher T , like Zr14) the solid migrates from cold to hot: T 2 > TI. Halogen lamps are based on this principle.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 259 3.1 1.3 Synthesis and Crystal Growth Under Controlled Thermodynamic 3.1 1.3.2 Chemical Vapor Transport of the Chalcogenides 1. J. Bloem, F. A. Kroger, Z . Phys. Chem., 7, l(1956). 2. F. A. Kroger, T h e Chemistry oflmperfect Crystals, Vol. I, North-Holland, Amsterdam, 1973. The best textbook in the field. Recommanded reading. 3. E. Kaldis, J . Cryst. Growth, 24/25, 53 (1974). 4. For high pressure synthesis see S. Porowski, J . Cryst. Growth, 166, 583 (1996) and therein mentioned literature. 5. A. C. Prior, J . Electrochem. Soc., 108, 82 (1961). 6. K. Igaki, S. Satoh, Jpn. J . Appl. Phys., 18, 1965 (1979); Trans. Jpn. Inst. Met., 13, 248 (1972). 7. T. Vamanaka, T. Shiraishi, Jpn. J . Appl. Phys., 4, 826 (1956). 8. M. M. Faktor, I. Garrett, Growth of Crystalsfrom the Vapor, Chapman & Hall, London, 1974. 9. R. A. Swalin, Thermodynamics of Solids, Wiley, New York, 1966.
3.11.3.2 Chemical Vapor Transport of the Chalcogenides Synthesis and crystal growth of chalcogenides (and many other compounds, e.g.; oxides) may also take place by chemical transport'. Such reactions lead to chemical mass transport if a solid can reversibly react with a gaseous reactant to yield a gaseous product, e.g.: ZnSe(s)
+ 12(g)+ Zn12(g)+ Se T2
T,
Cd4GeS6(s)
+ 512(g)+ 4Cd12 + Ge12 + 3S2
(b)
Upon application of a temperature gradient (AT = T 2 - TI),the chemical equilibrium is shifted so that chemical evaporation of the source takes place at T 2 and precipitation of the solid from the vapor phase at T1. Apart from unintentional doping with the transporting agent, which in some cases (e.g., group IIB-VIB compounds) influences the physical properties, chemical transport can be advantageous for preparative solid state chemistry: 1. Contrary to the direct reaction from the elements (see 3.1 1.3: solid vapor reaction), no
diffusional constraints appear in the presence of a chemical transporting agent. Thus if the thermodynamics of the reaction are known, homogeneous phases can be prepared. 2. Chemical evaporation takes place at appreciably lower temperatures than those of the corresponding sublimation. Thus crystals can be grown at lower temperatures (e.g., CdS and ZnSe melt at 1475 and 1520'C, respectively, and their corresponding decomposition pressures at mp are 3.8 and 0.53 atm). Crystals are grown by sublimation at ca. 1100°C. For chemical transport with 12, T 750°C is s ~ f f i c i e n t ~ . ~ .
-
Simple thermodynamic rules for chemical transport reactions are formulated'. The thermodynamic driving force of chemical transport is the shift of the chemical equilibrium (free energy of the reaction, AG = AGT2- AGT,) along the temperature gradient. In view of the reverse reaction, extreme values of the equilibrium constant are not suitable. Values of K r , / K T , = K z 1 (AG = - RT In K , N 0) are ideal. The transport takes place from high concentration of the volatile product (more negative AGT,) to lower concentration (less negative AGT,).For most reactions this appears when T I exceeds T 2 ,i.e., when the solid is migrating from hot to cold (endothermal transport; increasing vapor pressure of the volatile product with increasing T ) .For exothermic volatile products (i.e., decomposing at higher T , like Zr14) the solid migrates from cold to hot: T 2 > TI. Halogen lamps are based on this principle.
260
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 3.1 1.4 By Reactions in Chalcogen-Hydrogen Systems
The thermodynamic background for the control of the nonstoichiometry of transported sulfide’ crystals is described elsewhere4. The calculation is based on a binary transporting agent with components L j ( j = 1,2). The system has four components, two phases, and, therefore, four degrees of freedom. The main problem is the interdependence of the thermodynamic states of the compound AB, at the depositiom area ( T , ) and the source (TJ. Combination of an expression for the flux of the components with the mass conservation law leads to an expression for composition of the solid deposited at T1: JB flux of B - number of moles B deposited at T I J A flux of A - number of moles A deposited at T I
XT, = --
(4
which can be transformed to an expression of partial pressures, calculated from existing data:
xi
where P$ = v ~Pi,is ~the balance pressure for the element K = A, B, L1, .. . , L j with v ~the, stoichiometric ~ coefficients. Equation (d) allows calculation of the composition of the transported nonstoichiometric solid, where a change of stoichiometry is induced between source and deposit. Since the equation describes vapor phase compositions, it can also be used for chemical vapor deposition (CVD),where a solid (usually thin layer) is precipitated from a mixture of gases and vapors of given composition. Application of the above equations to the chemical transport of FeS, results in the phase relationships and the controlled growth of single crystals with compositions 1.133 < (mol S)/(mol Fe) < 1.095. Other transporting agents (HCI, HBr, H J , and Ge halides) are also investigated. Although ca. 200 ppm Ge is incorporated, no influence on the metal-to-semiconductor phase transition (see 3.1 1.2.1, Fig. 1) is found. Different thermodynamic analyses of the chemical transport have been compared’. (E. KALDIS) 1. H. Schaffer, Chemical Transport Reactions, Verlag Chemie, Weinheim, 1964. 2. E. Kaldis, J . Cryst. Growth, 9, 281 (1971); 24/25, 5 3 (1974). 3. E. Kaldis, J . Phys. Chem. Solids, 26, 1701 (1965). 4. E. Wolf, H. Opperman, G. Krabbes, W. Reichelt, in “Current Topics in Materials Science”, E. Kaldis, ed., 1, 697 (1978), North-Holland, Amsterdam, 1978. Review of chemical transport methods for crystal growth of nonstoichiometric FeS,. Recommended reading. 5. M. W. Richardson, B. I. Nolang, J . Cryst. Growth, 42, 90 (1977). 6. M. Saeki, J . Cryst. Growth, 36, 77 (1976). 7. G. Krabbes, H. Opperman, E. Wolf, J . Cryst. Growth, 64, 353, (1983).
3.1 1.4 By Reactions in Chalcogen-Hydrogen Systems Seldom is H2X (X = S, Se, Te) used to form nonstoichiometric chalcogenides, because reaction time and temperature must be carefully controlled to produce the desired single-phase material. Reactions are carried out in horizontal or vertical flow systems in which H2X is passed over the reactants. Reactants may be metals or their compounds, or they may be admixed with a flux. Usually the source of H2X is outside the
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
260
3.1 1 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 3.1 1.4 By Reactions in Chalcogen-Hydrogen Systems
The thermodynamic background for the control of the nonstoichiometry of transported sulfide’ crystals is described elsewhere4. The calculation is based on a binary transporting agent with components L j ( j = 1,2). The system has four components, two phases, and, therefore, four degrees of freedom. The main problem is the interdependence of the thermodynamic states of the compound AB, at the depositiom area ( T , ) and the source (TJ. Combination of an expression for the flux of the components with the mass conservation law leads to an expression for composition of the solid deposited at T1: JB flux of B - number of moles B deposited at T I J A flux of A - number of moles A deposited at T I
XT, = --
(4
which can be transformed to an expression of partial pressures, calculated from existing data:
xi
where P$ = v ~Pi,is ~the balance pressure for the element K = A, B, L1, .. . , L j with v ~the, stoichiometric ~ coefficients. Equation (d) allows calculation of the composition of the transported nonstoichiometric solid, where a change of stoichiometry is induced between source and deposit. Since the equation describes vapor phase compositions, it can also be used for chemical vapor deposition (CVD),where a solid (usually thin layer) is precipitated from a mixture of gases and vapors of given composition. Application of the above equations to the chemical transport of FeS, results in the phase relationships and the controlled growth of single crystals with compositions 1.133 < (mol S)/(mol Fe) < 1.095. Other transporting agents (HCI, HBr, H J , and Ge halides) are also investigated. Although ca. 200 ppm Ge is incorporated, no influence on the metal-to-semiconductor phase transition (see 3.1 1.2.1, Fig. 1) is found. Different thermodynamic analyses of the chemical transport have been compared’. (E. KALDIS)
H. Schaffer, Chemical Transport Reactions, Verlag Chemie, Weinheim, 1964. E. Kaldis, J . Cryst. Growth, 9, 281 (1971); 24/25, 5 3 (1974). E. Kaldis, J . Phys. Chem. Solids, 26, 1701 (1965). E. Wolf, H. Opperman, G. Krabbes, W. Reichelt, in “Current Topics in Materials Science”, E. Kaldis, ed., 1, 697 (1978), North-Holland, Amsterdam, 1978. Review of chemical transport methods for crystal growth of nonstoichiometric FeS,. Recommended reading. 5. M. W. Richardson, B. I. Nolang, J . Cryst. Growth, 42, 90 (1977). 6. M. Saeki, J . Cryst. Growth, 36, 77 (1976). 7. G. Krabbes, H. Opperman, E. Wolf, J . Cryst. Growth, 64, 353, (1983).
1. 2. 3. 4.
3.1 1.4 By Reactions in Chalcogen-Hydrogen Systems Seldom is H2X (X = S, Se, Te) used to form nonstoichiometric chalcogenides, because reaction time and temperature must be carefully controlled to produce the desired single-phase material. Reactions are carried out in horizontal or vertical flow systems in which H2X is passed over the reactants. Reactants may be metals or their compounds, or they may be admixed with a flux. Usually the source of H2X is outside the
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.4 By Reactions in Chatcogen-Hydrogen Systems 3.1 1.4.2 Of Compounds of Metals
261
reactor, although preparation in situ is occasionally performed (by passing H Z over the chalcogen in one part of the furnace while the reaction takes place downstream) as in the case of X = Te. The H2X gases are poisonous and must be absorbed in suitable solvents after emerging from the furnace. The apparatus should be situated in a fume hood. (P. K. DORHOUT, H. STEINFINK) 3.11.4.1 Of Metals
When H2S is passed over powdered Nb or Ta for 2 h at 300-1000"C, Nb1.6S2and a nonstoichiometric Ta compound are obtained. At 1400"C, TaS2 forms'. The phases Fe,S (0.85 < x < 1) form when powdered Fe is reacted in a current of HzS2. Members of a series of ReTel +, (0.04 < x < 1.475)are prepared by passing H2 over Te, which reacts with metallic Re in a separate container downstream in a tube furnace for 1-5 h at 750-900"C3. These phases are also prepared using the isopiestic method4. Copper wire is sulfided to study the thermodynamics of digenite solid solutions, Cu2-,S, at 600-1000°C by suspending the sample from a thermobalance in a silica crucible and recording weight changes in a variable H2S/H2 atmosphere'. (P. K. DORHOUT, H. STEINFINK) 1. S. V. Radzikovskaya, V. F. Bukhanevich, Khal'kogenidy, Scoistaa, Metody Poluch. Primen.,
2. 3. 4. 5.
Muter. Semin., Kiev, 1967, p. 58. M. Chevreton, B. Petit, S. Brunie, J. M. Kaufmann, C.R. Hebd. Seances Acad. Sci., 270,426 (1970). V. A. Obolonchik, A. A. Yanaki, Tr. Vses. Soaeshch. Probl. Reniya, Moscow, 1970, p. 59. R. Krachler, H. Ipser, Z. Metallkd., 87, 262 (1996). M. Nagamori, Metall. Muter. Trans., B, 7, 67 (1976).
3.11.4.2 Of Compounds of Metals
The Fe,S phases referred to in 3.11.4.1 (0.85 < x < 1) are also prepared from iron chloride, sulfate, or nitrate', and the ReTe, +, phases form from ammonium perhenate' by action of H2X. Mixed rare earth (Ln) chalcogenides form when H2Sis passed over the sesquiselenides (Ln2Se3)to obtain Ln2S2(SeSe,) and Ln2S2(SSe,)3.Mixed transition metal dichalcogenides are obtained by chemical transport reactions. Hydrogen bronzes of MoS2 form by reaction of H2S/H2 with (NH4)2MoS4,giving H,MoS2 (0.012 < x < 0.84)4. Solid (NH4)2MoS45is heated abruptly from 295 to 623 K in a flowing mixture of 14% H2S in H2.The resulting solid is heated for 1 h at 673 K in H2. Metal oxides contained in graphite crucibles are treated in an H2S atmosphere at 1150'C and annealed at 800°C to obtain single-phase materials of composition Me,NbS2 and Me,TaS2 (x z 0.25; Me = Mn, Cr). The phases Me,NbS2 (x FZ 0.3333) form when Me = V, Mn, Fe, Co, and Ni. Analogous Ta compounds are prepared with Fe, Co, and Ni6. A vanadium sulfide catalyst of unknown composition forms upon bubbling H2S through a solution of V 2 0 s dissolved in NaOH'. A series of incommensurate structures based on the BaNi0,-type structure are prepared by modification of the H2S method using CS2 as the sulfiding agent. Sr,TiS3 (1.05 < x < 1.22) forms by reacting SrC03 and T i 0 2 in a stream of CS2 in N2 at 700-900"C8. A sulfur-deficient solid, BaNbS3+, (x = 0.11) forms when BaC03 and N b 0 2 are reacted at elevated temperatures yielding BaNb03, which is then sulfided by
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.4 By Reactions in Chatcogen-Hydrogen Systems 3.1 1.4.2 Of Compounds of Metals
261
reactor, although preparation in situ is occasionally performed (by passing H Z over the chalcogen in one part of the furnace while the reaction takes place downstream) as in the case of X = Te. The H2X gases are poisonous and must be absorbed in suitable solvents after emerging from the furnace. The apparatus should be situated in a fume hood. (P. K. DORHOUT, H. STEINFINK) 3.11.4.1 Of Metals
When H2S is passed over powdered Nb or Ta for 2 h at 300-1000"C, Nb1.6S2and a nonstoichiometric Ta compound are obtained. At 1400"C, TaS2 forms'. The phases Fe,S (0.85 < x < 1) form when powdered Fe is reacted in a current of HzS2. Members of a series of ReTel +, (0.04 < x < 1.475)are prepared by passing H2 over Te, which reacts with metallic Re in a separate container downstream in a tube furnace for 1-5 h at 750-900"C3. These phases are also prepared using the isopiestic method4. Copper wire is sulfided to study the thermodynamics of digenite solid solutions, Cu2-,S, at 600-1000°C by suspending the sample from a thermobalance in a silica crucible and recording weight changes in a variable H2S/H2 atmosphere'. (P. K. DORHOUT, H. STEINFINK) 1. S. V. Radzikovskaya, V. F. Bukhanevich, Khal'kogenidy, Scoistaa, Metody Poluch. Primen.,
2. 3. 4. 5.
Muter. Semin., Kiev, 1967, p. 58. M. Chevreton, B. Petit, S. Brunie, J. M. Kaufmann, C.R. Hebd. Seances Acad. Sci., 270,426 (1970). V. A. Obolonchik, A. A. Yanaki, Tr. Vses. Soaeshch. Probl. Reniya, Moscow, 1970, p. 59. R. Krachler, H. Ipser, Z. Metallkd., 87, 262 (1996). M. Nagamori, Metall. Muter. Trans., B, 7, 67 (1976).
3.11.4.2 Of Compounds of Metals
The Fe,S phases referred to in 3.11.4.1 (0.85 < x < 1) are also prepared from iron chloride, sulfate, or nitrate', and the ReTe, +, phases form from ammonium perhenate' by action of H2X. Mixed rare earth (Ln) chalcogenides form when H2Sis passed over the sesquiselenides (Ln2Se3)to obtain Ln2S2(SeSe,) and Ln2S2(SSe,)3.Mixed transition metal dichalcogenides are obtained by chemical transport reactions. Hydrogen bronzes of MoS2 form by reaction of H2S/H2 with (NH4)2MoS4,giving H,MoS2 (0.012 < x < 0.84)4. Solid (NH4)2MoS45is heated abruptly from 295 to 623 K in a flowing mixture of 14% H2S in H2.The resulting solid is heated for 1 h at 673 K in H2. Metal oxides contained in graphite crucibles are treated in an H2S atmosphere at 1150'C and annealed at 800°C to obtain single-phase materials of composition Me,NbS2 and Me,TaS2 (x z 0.25; Me = Mn, Cr). The phases Me,NbS2 (x FZ 0.3333) form when Me = V, Mn, Fe, Co, and Ni. Analogous Ta compounds are prepared with Fe, Co, and Ni6. A vanadium sulfide catalyst of unknown composition forms upon bubbling H2S through a solution of V 2 0 s dissolved in NaOH'. A series of incommensurate structures based on the BaNi0,-type structure are prepared by modification of the H2S method using CS2 as the sulfiding agent. Sr,TiS3 (1.05 < x < 1.22) forms by reacting SrC03 and T i 0 2 in a stream of CS2 in N2 at 700-900"C8. A sulfur-deficient solid, BaNbS3+, (x = 0.11) forms when BaC03 and N b 0 2 are reacted at elevated temperatures yielding BaNb03, which is then sulfided by
262
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.5 By Precipitation Under Normal and Supercritical Conditions 3.1 1.5.1 From Aqueous Solution
exposure to CS2/N2 at 500°C for 12 h and at 900°C for 24 h9. The solid is then placed into an evacuated ampule that is necked down in the middle and sealed with a piece of Ag metal in the cold end of the tube. The ampule is placed into a two-zone furnace (70O-60O3C, 24 h) with the BaNbS3 at the hot end. Other incommensurate solids have been prepared by action of H2S on binary oxide mixtures". LaCr03 and La203 are combined in a graphite boat and heated to 1300-1350°C in flowing Ar/H2S gas for 2-4 h, yielding (LaS)I,,,CrS2. (P. K. DORHOUT, H. STEINFINK) 1. M. Chevreton, B. Petit, S. Brunie, J. M. Kaufmann, C. R. Hebd. Seances Acad. Sci., 270, 426 (1970). 2. V. A. Obolonchik, A. A. Yanaki, Tr. Vses. Soceshch. Probl. Reniya, Moscow, 1970, p. 59 3. J. Loriers, G. Collin, Colloq. Int. C. N . R. S., 157, 407 (1967). 4. T. Komatsu, W. K. Hall, J . Phys. Chem., 96, 8131 (1992). 5. A. I. Hadjikyriacou, D. Coucouvanis, Inorg. Synth., 27, 39 (1990). 6. B. van Laar, H. M. Rietveld, D. J. W. Ido, J . Solid State Chem., 3, 154 (1971). 7. J. G. Gatsis. U. S. Patent 4,197,191; Chem. Abstr., 93, 117049 (1979). 8. M. Saeki, M. Onoda, M. Ohta, Mater. Res. Bull., 28, 279 (1993). 9. J. Yan, K. V. Ramanujachary, M. Greenblatt, Muter. Res. Bull., 30, 463 (1995). 10. J. Rouxel, A. Meerschaut, G. A. Wiegers, J . Alloys Compd., 229, 144 (1995).
3.11.5 By Precipitation Under Normal and Supercritical Conditions Solution reactions generally yield stoichiometric kinetic products, since the conditions are not extreme enough to create defect structures, However, the thermodynamically stable phases that form are often poorly crystalline. Critical fluid conditions have improved solvation abilities for both reagents and products and often afford crystalline phases. Despite the popular use of subcritical or critical solvent systems, there are few examples of nonstoichiometric solids formed by precipitation methods from either ambient or superambient conditions. Critical or supercritical solution reactions with chalcogenides are often performed in glass ampules, either contained in steel autoclaves (and counterpressured) or allowed to react under controlled and shielded conditions with small solvent volumes. Critical pressures for H 2 0 and NH3, for example, are 218 and 112 atm, respectively. These and other ambient pressure synthetic methods for selenides and tellurides have been reviewed'. (P. K. DORHOUT, H. STEINFINK)
1. L. C. Roof, J. W. Kolis, Chem. Rec., 93, 1037 (1993).
3.11.5.1 From Aqueous Solution
Nearly all procedures that employ aqueous media for precipitation of nonstoichiometric sulfides are aimed at an elucidation of the various stages and kinetics of corrosion of metals'. Gels of Fe(OH)3are treated with H2Sto prepare chromatographic columns containing FeS of indefinite composition'. When washed with H 2 0 , alkali transition metal sulfides form hydrates, A,(H20),MS2 Nao.33TaS2forms from action of 0.1 M aqueous Na2S204on TaSz at room temperature4.
'.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
262
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.5 By Precipitation Under Normal and Supercritical Conditions 3.1 1.5.1 From Aqueous Solution
exposure to CS2/N2 at 500°C for 12 h and at 900°C for 24 h9. The solid is then placed into an evacuated ampule that is necked down in the middle and sealed with a piece of Ag metal in the cold end of the tube. The ampule is placed into a two-zone furnace (70O-60O3C, 24 h) with the BaNbS3 at the hot end. Other incommensurate solids have been prepared by action of H2S on binary oxide mixtures". LaCr03 and La203 are combined in a graphite boat and heated to 1300-1350°C in flowing Ar/H2S gas for 2-4 h, yielding (LaS)I,,,CrS2. (P. K. DORHOUT, H. STEINFINK) 1. M. Chevreton, B. Petit, S. Brunie, J. M. Kaufmann, C. R. Hebd. Seances Acad. Sci., 270, 426 (1970). 2. V. A. Obolonchik, A. A. Yanaki, Tr. Vses. Soceshch. Probl. Reniya, Moscow, 1970, p. 59 3. J. Loriers, G. Collin, Colloq. Int. C. N . R. S., 157, 407 (1967). 4. T. Komatsu, W. K. Hall, J . Phys. Chem., 96, 8131 (1992). 5. A. I. Hadjikyriacou, D. Coucouvanis, Inorg. Synth., 27, 39 (1990). 6. B. van Laar, H. M. Rietveld, D. J. W. Ido, J . Solid State Chem., 3, 154 (1971). 7. J. G. Gatsis. U. S. Patent 4,197,191; Chem. Abstr., 93, 117049 (1979). 8. M. Saeki, M. Onoda, M. Ohta, Mater. Res. Bull., 28, 279 (1993). 9. J. Yan, K. V. Ramanujachary, M. Greenblatt, Muter. Res. Bull., 30, 463 (1995). 10. J. Rouxel, A. Meerschaut, G. A. Wiegers, J . Alloys Compd., 229, 144 (1995).
3.11.5 By Precipitation Under Normal and Supercritical Conditions Solution reactions generally yield stoichiometric kinetic products, since the conditions are not extreme enough to create defect structures, However, the thermodynamically stable phases that form are often poorly crystalline. Critical fluid conditions have improved solvation abilities for both reagents and products and often afford crystalline phases. Despite the popular use of subcritical or critical solvent systems, there are few examples of nonstoichiometric solids formed by precipitation methods from either ambient or superambient conditions. Critical or supercritical solution reactions with chalcogenides are often performed in glass ampules, either contained in steel autoclaves (and counterpressured) or allowed to react under controlled and shielded conditions with small solvent volumes. Critical pressures for H 2 0 and NH3, for example, are 218 and 112 atm, respectively. These and other ambient pressure synthetic methods for selenides and tellurides have been reviewed'. (P. K. DORHOUT, H. STEINFINK)
1. L. C. Roof, J. W. Kolis, Chem. Rec., 93, 1037 (1993).
3.11.5.1 From Aqueous Solution
Nearly all procedures that employ aqueous media for precipitation of nonstoichiometric sulfides are aimed at an elucidation of the various stages and kinetics of corrosion of metals'. Gels of Fe(OH)3are treated with H2Sto prepare chromatographic columns containing FeS of indefinite composition'. When washed with H 2 0 , alkali transition metal sulfides form hydrates, A,(H20),MS2 Nao.33TaS2forms from action of 0.1 M aqueous Na2S204on TaSz at room temperature4.
'.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
262
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.5 By Precipitation Under Normal and Supercritical Conditions 3.1 1.5.1 From Aqueous Solution
exposure to CS2/N2 at 500°C for 12 h and at 900°C for 24 h9. The solid is then placed into an evacuated ampule that is necked down in the middle and sealed with a piece of Ag metal in the cold end of the tube. The ampule is placed into a two-zone furnace (70O-60O3C, 24 h) with the BaNbS3 at the hot end. Other incommensurate solids have been prepared by action of H2S on binary oxide mixtures". LaCr03 and La203 are combined in a graphite boat and heated to 1300-1350°C in flowing Ar/H2S gas for 2-4 h, yielding (LaS)I,,,CrS2. (P. K. DORHOUT, H. STEINFINK) 1. M. Chevreton, B. Petit, S. Brunie, J. M. Kaufmann, C. R. Hebd. Seances Acad. Sci., 270, 426 (1970). 2. V. A. Obolonchik, A. A. Yanaki, Tr. Vses. Soceshch. Probl. Reniya, Moscow, 1970, p. 59 3. J. Loriers, G. Collin, Colloq. Int. C. N . R. S., 157, 407 (1967). 4. T. Komatsu, W. K. Hall, J . Phys. Chem., 96, 8131 (1992). 5. A. I. Hadjikyriacou, D. Coucouvanis, Inorg. Synth., 27, 39 (1990). 6. B. van Laar, H. M. Rietveld, D. J. W. Ido, J . Solid State Chem., 3, 154 (1971). 7. J. G. Gatsis. U. S. Patent 4,197,191; Chem. Abstr., 93, 117049 (1979). 8. M. Saeki, M. Onoda, M. Ohta, Mater. Res. Bull., 28, 279 (1993). 9. J. Yan, K. V. Ramanujachary, M. Greenblatt, Muter. Res. Bull., 30, 463 (1995). 10. J. Rouxel, A. Meerschaut, G. A. Wiegers, J . Alloys Compd., 229, 144 (1995).
3.11.5 By Precipitation Under Normal and Supercritical Conditions Solution reactions generally yield stoichiometric kinetic products, since the conditions are not extreme enough to create defect structures, However, the thermodynamically stable phases that form are often poorly crystalline. Critical fluid conditions have improved solvation abilities for both reagents and products and often afford crystalline phases. Despite the popular use of subcritical or critical solvent systems, there are few examples of nonstoichiometric solids formed by precipitation methods from either ambient or superambient conditions. Critical or supercritical solution reactions with chalcogenides are often performed in glass ampules, either contained in steel autoclaves (and counterpressured) or allowed to react under controlled and shielded conditions with small solvent volumes. Critical pressures for H 2 0 and NH3, for example, are 218 and 112 atm, respectively. These and other ambient pressure synthetic methods for selenides and tellurides have been reviewed'. (P. K. DORHOUT, H. STEINFINK)
1. L. C. Roof, J. W. Kolis, Chem. Rec., 93, 1037 (1993).
3.11.5.1 From Aqueous Solution
Nearly all procedures that employ aqueous media for precipitation of nonstoichiometric sulfides are aimed at an elucidation of the various stages and kinetics of corrosion of metals'. Gels of Fe(OH)3are treated with H2Sto prepare chromatographic columns containing FeS of indefinite composition'. When washed with H 2 0 , alkali transition metal sulfides form hydrates, A,(H20),MS2 Nao.33TaS2forms from action of 0.1 M aqueous Na2S204on TaSz at room temperature4.
'.
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 263 3.11.5 By Precipitation Under Normal and Supercritical Conditions 3.11.5.2 From Nonaqueous Solution
Small particulate metal sulfides with unknown or ill-defined stoichiometries, nanoparticles and nanoclusters, are made in lipid bilayers, a precipitation reaction within a confined space5. Bovine brain phosphatidylserine, glyceryl monooleate, and a polymerizable surfactant react in decanol with 1% EtOH. The bilayer is established across a small hole in a Teflon sheet, and MC12 solutions (M = Cd, Zn) are introduced into the bilayer by diffusion from aqueous solutions. The sulfide forms upon injection of H2S gas into the solution on the opposite side of the bilayer membrane. Similar nanoparticles of MS solids are grown in the cavities within zeolites6 or porous membranes', with polysulfide or H2S solutions acting on the impregnated solids. Aqueous or hydrothermal reactions at high temperature and pressure yield nonstoichiometric metal sulfides and selenides8-12.Generally, simple or complex chalcogenides form when the elements or metals and alkali metal polychalcogenide salts are combined in sealed glass reactors. Heating for several days to 200°C (under guarded conditions as pressures within glass ampules at this temperature are tens of atmospheres) affords reaction. Several nonstoichiometric Mo sulfides and selenides are prepared by 4 this method, e.g., ((NH,), [M03S11,72Se1,28])2[sel,] is made from ( N H 4 ) 2 M ~ Sand NaS3Se3,a compound that contains a unique Se12 neutral ring13. (P. K. DORHOUT, H. STEINFINK) 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.
D. W. Shoesmith, P. Taylor, M. G. Bailey, D. G. Owen, J. Electrochem. Soc., 127, 1007 (1980). R. Caletka, J . Chromatogr., 111, 93 (1975). R. Schollhorn, A. Lerf, J . Less-Common Met., 42, 89 (1975). R. Schollhorn, E. Sick, A. Lerf, Muter. Res. Bull., 10, 1005 (1975). S. Baral, X. K. Zhao, R. Rolandi, J. H. Fendler, J . Phys. Chem., 91, 2701 (1987). N. Herron, Y. Wang, M. M. Eddy, G. D. Stucky, D. E. Cox, K. Moller, T. Bein, J . Am. Chem. Soc., I l l , 530 (1989). C. M. Zelenski, G. L. Hornyak, P. K. Dorhout, Nanostruct. Mater., 9, 173 (1997). L. Cambi, M. Elli, Chim. Ind. (Milan),50, 94 (1968). V. I. Popolitov, Inorg. Muter., 26, 1180 (1990). A. Flamini, 0. Grubessi, Peroid. Mineral. A , 39, 243 (1970). L. Cambi, M. Elli, Chim.Ind. (Milan),50, 869 (1968). W. S. Sheldrick, Z . Anorg. Allg. Chem., 562, 23 (1988). R. A. Stevens, C. C. Raymond, P. K. Dorhout, Angew. Chem., Int. Ed. Eng., 34, 2509 (1995).
3.1 1.5.2 From Nonaqueous Solution
Thin films formed by sulfidation of Cu by S dissolved in benzene near room temperature have compositions like Cu2-*S (0.18 < x < 0.45) and Cu1.97S1.Electrochemical procedures are frequently used to study formation kinetics and thermodynamic parameters for nonstoichiometric sulfides. These are discussed in 3.11.6. Alkali metal dichalcogenides form by dissolving MS2 in blue alkali N H 3 solutions. The compounds A,MS2 x = 0.5-0.8, A = Li, Na, K, Rb, Cs, M = Ti, Mo, W, Re) form2. Three distinct phases of Na,TiS2 are obtained from solutions of N a in liquid NH3 (0.79 < x < 1, 0.38 < x < 0.72, and 0.17 < x < 0.33). Blue Na or K [(CH3)2N]3P0 solutions are used to prepare Na,TaS2 and K,TaS2 3 , 4 . Other intercalates of TaS2 with organic compounds and alkali metal hydroxides are accessible5; e.g., [Fe6S8(P(C2H5)3)3]0,05TaS2 forms in reaction of Na,,33TaS2with water-N-methylformamide solutions of [Fe6s8(P(C,H5)3)3]2' at room temperature6. Lithiation of MS2 (M = Ti, Mo, W) using n-BuLi in hexanes yields Li,MS2, (0.3 < x < 1.3)7.Compounds with higher x values (x z 1.45) are obtained by heating the
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 263 3.11.5 By Precipitation Under Normal and Supercritical Conditions 3.11.5.2 From Nonaqueous Solution
Small particulate metal sulfides with unknown or ill-defined stoichiometries, nanoparticles and nanoclusters, are made in lipid bilayers, a precipitation reaction within a confined space5. Bovine brain phosphatidylserine, glyceryl monooleate, and a polymerizable surfactant react in decanol with 1% EtOH. The bilayer is established across a small hole in a Teflon sheet, and MC12 solutions (M = Cd, Zn) are introduced into the bilayer by diffusion from aqueous solutions. The sulfide forms upon injection of H2S gas into the solution on the opposite side of the bilayer membrane. Similar nanoparticles of MS solids are grown in the cavities within zeolites6 or porous membranes', with polysulfide or H2S solutions acting on the impregnated solids. Aqueous or hydrothermal reactions at high temperature and pressure yield nonstoichiometric metal sulfides and selenides8-12.Generally, simple or complex chalcogenides form when the elements or metals and alkali metal polychalcogenide salts are combined in sealed glass reactors. Heating for several days to 200°C (under guarded conditions as pressures within glass ampules at this temperature are tens of atmospheres) affords reaction. Several nonstoichiometric Mo sulfides and selenides are prepared by 4 this method, e.g., ((NH,), [M03S11,72Se1,28])2[sel,] is made from ( N H 4 ) 2 M ~ Sand NaS3Se3,a compound that contains a unique Se12 neutral ring13. (P. K. DORHOUT, H. STEINFINK) 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.
D. W. Shoesmith, P. Taylor, M. G. Bailey, D. G. Owen, J. Electrochem. Soc., 127, 1007 (1980). R. Caletka, J . Chromatogr., 111, 93 (1975). R. Schollhorn, A. Lerf, J . Less-Common Met., 42, 89 (1975). R. Schollhorn, E. Sick, A. Lerf, Muter. Res. Bull., 10, 1005 (1975). S. Baral, X. K. Zhao, R. Rolandi, J. H. Fendler, J . Phys. Chem., 91, 2701 (1987). N. Herron, Y. Wang, M. M. Eddy, G. D. Stucky, D. E. Cox, K. Moller, T. Bein, J . Am. Chem. Soc., I l l , 530 (1989). C. M. Zelenski, G. L. Hornyak, P. K. Dorhout, Nanostruct. Mater., 9, 173 (1997). L. Cambi, M. Elli, Chim. Ind. (Milan),50, 94 (1968). V. I. Popolitov, Inorg. Muter., 26, 1180 (1990). A. Flamini, 0. Grubessi, Peroid. Mineral. A , 39, 243 (1970). L. Cambi, M. Elli, Chim.Ind. (Milan),50, 869 (1968). W. S. Sheldrick, Z . Anorg. Allg. Chem., 562, 23 (1988). R. A. Stevens, C. C. Raymond, P. K. Dorhout, Angew. Chem., Int. Ed. Eng., 34, 2509 (1995).
3.1 1.5.2 From Nonaqueous Solution
Thin films formed by sulfidation of Cu by S dissolved in benzene near room temperature have compositions like Cu2-*S (0.18 < x < 0.45) and Cu1.97S1.Electrochemical procedures are frequently used to study formation kinetics and thermodynamic parameters for nonstoichiometric sulfides. These are discussed in 3.11.6. Alkali metal dichalcogenides form by dissolving MS2 in blue alkali N H 3 solutions. The compounds A,MS2 x = 0.5-0.8, A = Li, Na, K, Rb, Cs, M = Ti, Mo, W, Re) form2. Three distinct phases of Na,TiS2 are obtained from solutions of N a in liquid NH3 (0.79 < x < 1, 0.38 < x < 0.72, and 0.17 < x < 0.33). Blue Na or K [(CH3)2N]3P0 solutions are used to prepare Na,TaS2 and K,TaS2 3 , 4 . Other intercalates of TaS2 with organic compounds and alkali metal hydroxides are accessible5; e.g., [Fe6S8(P(C2H5)3)3]0,05TaS2 forms in reaction of Na,,33TaS2with water-N-methylformamide solutions of [Fe6s8(P(C,H5)3)3]2' at room temperature6. Lithiation of MS2 (M = Ti, Mo, W) using n-BuLi in hexanes yields Li,MS2, (0.3 < x < 1.3)7.Compounds with higher x values (x z 1.45) are obtained by heating the
264 3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.11.6 By Insertion Reactions from Solutions
MSz/BuLi/hexanes mixtures in sealed ampules at temperatures as high as 100cCs.Other nonaqueous solvent routes include using ABH4 salts [A = Li, Na, K, or (R4N)] in pyridine, MeOH, or EtOH to prepare A,TaS, and A,TiSz9. (P. K. DORHOUT, H. STEINFINK)
1. 2. 3. 4. 5. 6. 7. 8. 9.
C. Labar, R. Breckpot, Bull. SOC.Chim. Belg., 81, 565 (1972). W. Rudorff, Chimia, 19, 489 (1965). J. Rouxel, M. Danot, J. Bichon, Bull. SOC.Chem. Fr., 11, 3930 (1971). J. Rouxel, L. Trichet, P. Chevalier, P. Colombet, 0. A. Ghaloun, J . Solid State Chem., 29, 3 11 (1979). 0. Matsumoto, E. Yamada, Y. Kanzaki, M. Konuma, J . Phys. Chem. Solids, 39, 191 (1978). L. F. Nazar, A. J. Jacobson, J . Chem. SOC.,Chem. Commun., 570 (1986). D. W. Murphy, F. J. DiSalvo, G. W. Hull, J. V. Waszczak, Inorg. Chem., 15, 17 (1976). D. Yang, R. F. Frindt, J . Phys. Chem. Solids, 57, 1113 (1996). M. G. Kanatzidis, T. J. Marks, Inorg. Chem., 26, 783 (1986).
3.1 1.6 By Insertion Reactions from Solutions The term “Einlagerung” was first used to describe reactions in which atoms or ions are inserted into a solid without severe changes in its crystal structure and lattice dimensions. Products of these reactions have been called “Einlagerungsverbindungen” or “interstitial compounds”. Characteristic examples are the hydrides, the carbides, or the nitrides of the early transition metals. In most of these the ratio of the inserted atoms with respect to the host lattice is nonstoichiometric’s2. Since the graphite compounds also show nonstoichiometric ratios between the host and the guest components and since there are also topological relations between the starting materials and the end products, the term “einlagerungsverbindung” has been applied to graphite-alkali-metal compounds3 and to all chemical derivatives of graphite4. The term “intercalation” is used in the same sense as earlier the term “einlagerung”; however, the term “interstitial compounds” has also been used to name these compounds5. Peculiar for compounds undergoing intercalation/deintercalation processes is the non random distribution of interstitial sites in special zones within the crystal structure, e.g., in two-dimensional arrays or in one-dimensional channels (running parallel through the structure or intersecting each other). In most of these compounds there are more empty lattice sites than can be occupied by atoms, allowing the mobility of the interstitial atoms to be very high if their interaction with the host structure is weak. Many intercalation reactions can be carried out at RT (or slightly above), making accessible new compounds that are not stable at high temperatures. Thus a new field of solid state chemistry, the “soft chemistry,” has been created, referring to the very mild reaction conditions, unusual in solid state chemistry6. With the layered or chain host lattices, the expansion of the lattice in one or two dimensions is not seriously restricted, allowing the accommodation of species other than atoms (e.g., metal complexes, organic cations). It is possible that the inserted metal atoms trigger the uptake of suitable solvent molecules. These reactions have no counterpart in classic nonstoichiometric compounds, justifying the introduction of a new term. Thus the term “intercalation” compounds is understood nowadays in a much broader sense: intercalation is considered as the reversible uptake of atoms, ions, molecular cations, or molecules at low temperature while the structure of the host lattices is conserved.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
264 3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.11.6 By Insertion Reactions from Solutions
MSz/BuLi/hexanes mixtures in sealed ampules at temperatures as high as 100cCs.Other nonaqueous solvent routes include using ABH4 salts [A = Li, Na, K, or (R4N)] in pyridine, MeOH, or EtOH to prepare A,TaS, and A,TiSz9. (P. K. DORHOUT, H. STEINFINK)
1. 2. 3. 4. 5. 6. 7. 8. 9.
C. Labar, R. Breckpot, Bull. SOC.Chim. Belg., 81, 565 (1972). W. Rudorff, Chimia, 19, 489 (1965). J. Rouxel, M. Danot, J. Bichon, Bull. SOC.Chem. Fr., 11, 3930 (1971). J. Rouxel, L. Trichet, P. Chevalier, P. Colombet, 0. A. Ghaloun, J . Solid State Chem., 29, 3 11 (1979). 0. Matsumoto, E. Yamada, Y. Kanzaki, M. Konuma, J . Phys. Chem. Solids, 39, 191 (1978). L. F. Nazar, A. J. Jacobson, J . Chem. SOC.,Chem. Commun., 570 (1986). D. W. Murphy, F. J. DiSalvo, G. W. Hull, J. V. Waszczak, Inorg. Chem., 15, 17 (1976). D. Yang, R. F. Frindt, J . Phys. Chem. Solids, 57, 1113 (1996). M. G. Kanatzidis, T. J. Marks, Inorg. Chem., 26, 783 (1986).
3.1 1.6 By Insertion Reactions from Solutions The term “Einlagerung” was first used to describe reactions in which atoms or ions are inserted into a solid without severe changes in its crystal structure and lattice dimensions. Products of these reactions have been called “Einlagerungsverbindungen” or “interstitial compounds”. Characteristic examples are the hydrides, the carbides, or the nitrides of the early transition metals. In most of these the ratio of the inserted atoms with respect to the host lattice is nonstoichiometric’s2. Since the graphite compounds also show nonstoichiometric ratios between the host and the guest components and since there are also topological relations between the starting materials and the end products, the term “einlagerungsverbindung” has been applied to graphite-alkali-metal compounds3 and to all chemical derivatives of graphite4. The term “intercalation” is used in the same sense as earlier the term “einlagerung”; however, the term “interstitial compounds” has also been used to name these compounds5. Peculiar for compounds undergoing intercalation/deintercalation processes is the non random distribution of interstitial sites in special zones within the crystal structure, e.g., in two-dimensional arrays or in one-dimensional channels (running parallel through the structure or intersecting each other). In most of these compounds there are more empty lattice sites than can be occupied by atoms, allowing the mobility of the interstitial atoms to be very high if their interaction with the host structure is weak. Many intercalation reactions can be carried out at RT (or slightly above), making accessible new compounds that are not stable at high temperatures. Thus a new field of solid state chemistry, the “soft chemistry,” has been created, referring to the very mild reaction conditions, unusual in solid state chemistry6. With the layered or chain host lattices, the expansion of the lattice in one or two dimensions is not seriously restricted, allowing the accommodation of species other than atoms (e.g., metal complexes, organic cations). It is possible that the inserted metal atoms trigger the uptake of suitable solvent molecules. These reactions have no counterpart in classic nonstoichiometric compounds, justifying the introduction of a new term. Thus the term “intercalation” compounds is understood nowadays in a much broader sense: intercalation is considered as the reversible uptake of atoms, ions, molecular cations, or molecules at low temperature while the structure of the host lattices is conserved.
3.1 1 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.6 By Insertion Reactions from Solutions
265
“Intercalation” does not tell anything about the nature of the chemical reaction underlying this process. The term stresses mainly the topological relationships between the host and the end product of the reaction. The chemical reactions involved can be redox processes as in the case of intercalation in noncharged host lattices, or ion exchange and solvation reactions (adsorption processes) in the case of ternary compounds with negatively charged host lattices. The following discussion stresses the insertion reactions carried out in solutions, but for completeness, high temperature reactions also are mentioned. A general overview of intercalation reactions in chalcogenides is given in Scheme 1. With the exception of iodine intercalation into TaSe, or NbSeL almost all insertion processes in neutral chalcogenide host lattices are accompanied with a reduction of the host (pathway l)6,7.This is achieved by treatment of the host with the metals to be intercalated. An alternative method involves preparation of the samples directly from the elements (Scheme 1, pathway 3). A very new and promising method for producing intercalated crystals is the metal deposition on the solid host substrate in ultrahigh vacuum systems. This method has been applied recently mainly for intercalation of alkali metals but also Cu or Ag8-”.
Scheme 1. General overview on the reaction pathways of intercalation chemistry: “host” means any neutral host lattice accessible to redox reactions accompanied with insertion of I (intercalated species; mostly cations) and a charge transfer to the host. The reactions in the shadowed array are restricted to two-dimensional and chainlike host lattices; “solv” means solvent taken up in the interstitial space.
266
3.11 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 3.1 1.6 By Insertion Reactions from Solutions
Alkali metals, alkaline earth metals and Eu and Y can be intercalated from their NH3 or their hexamethylphosphoric triamide (HMPA) solutions. Reduction reactions can be conducted by applying chemical reducing agents or by electrochemical intercalation7% 133 14. In both cases, the metals are taken up as cations from solutions. Avoiding solvent uptake affords use of nonaqueous solvents. Solvent cointercalation is not a problem for chalcogenides with framework or channel-containing structures, if the channels are large enough to take up the unsolvated ions only. To avoid contamination with additional chemicals during chemical reduction, it is reasonable to use salts whose anion acts as a reducing agent. The most widely used system for chemical reduction is n-butyllithium dissolved in hexane, which does not cointercalate. It has been used in a screening for solid compounds suitable for the application as battery catho d e ~ ‘ ~These . methods are applied mainly at RT; thus the only cations that can be intercalated are those having high enough mobility in the interlayer gap. The limitation of temperature, solvents, and possible solutes, restrict application of these methods to a few cations (Li, Na, Ag, Cu). The temperature range of the electrochemical reduction can be extended to about 150°C (in solvents like ethylencarbonate) or to higher temperatures (if fused salt mixtures are used as the electrolyte)’5. The chemical and electrochemical reduction pathway also allows intercalation of organic or organometallic cations from solutions (see 3.11.6.1.7).It is debatable whether the intercalation of neutral nitrogen-containing molecules is in general accompanied by a redox process (see 3.11.6.1.6). Reacton l a of Scheme 1 allows the additional uptake of a second cation if further electrons can be transferred to the conduction band of the host and if there are empty lattice sites apart from the sites occupied by 1’. The methods used for this “cointercaiation” are like that described for intercalation in neutral host lattices. Since many intercalation reactions are reversible, the oxidative deintercalation of cations (Scheme 1, pathway 2) leads back to the starting materials (the full reversibility is an idealization). This method is of special interest for preparing new neutral host lattices that cannot be prepared from the elements by high temperature reactions because they tend to form nonstoichiometric compounds or to be unstable at high temperature. These new neutral host lattices are accessible for further modifications by intercalation reactions. Starting materials are ternary or multinary compounds containing cations of at least moderate ion mobility, whereas the counterions are structural building elements like layers, chains, or three-dimensional frameworks. The deintercalation is carried out by chemical oxidation (e.g., by iodine in acetonitrile) or by electrochemical methods. Table 1’6-35 gives a collection of such metastable host lattices, their starting materials, and the principal way for deintercalation. Alkali metal and alkaline earth metal intercalation compounds A,[M,X,] of layered or chainlike host lattice structures undergo solvation reactions with HzO or other highly polar solvents showing a high solvation capacity of cations, if the negative charge of the host lattice (and, vice versa the content of the charge compensating cations) is not too high (reaction pathway 4). Apart from the strength of the Coulomb interaction, free accessible space is necessary for the uptake of solvents. Some ternary compounds take up solvents if the charge of the structure building units is reduced to a suitable extent (e.g., KCrSz, LiVS2, K2Pt4S6).Since the chalcogenides are sensitive to redox reactions, the solvents must be stable against reduction; e.g., H z O can be reduced easily, and it reacts with alkali intercalation compounds of the dichalcogenides under H2 evolution and partial deintercalation of the cations (see 3.11.6.1.5).
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.6 By Insertion Reactions from Solutions
267
TABLE1. METASTABLE CHALCOGENIDES OBTAINED BY DEINTERCALATION REACTIONS
Metastable product
Starting Material
CrS2 CrSe,
vs2
LiVS2 KCrS, KCrSe,
IT-MoS~
KMoS~
Deintercalation Procedure I,/acetonitrile Oxygen, mineral acids Oxygen, mineral acids I, /acetonitrile 1. H 2 0 ; partial deintercalation to
Ref.
17 18 18 19 20
K0.33(H20)0.6MoS2
2. Oxidation of Kn.33(H20)n.6MoS2 by I,/acetonitrile (or electrochemical oxidation) 0.1 N K 2 C r 2 0 7in 0.1 N aqueous H 2 S 0 4 0.1 N K 2 C r 2 0 7in 0.1 N aqueous H 2 S 0 4 HC1; I,/acetonitrile Mineral acid, electrochemical oxidation Electrochemical Aqueous FeC1,; electrochemically HCl HC1, 400°C Mo15Se19 Two modifications M015S19 Ti3S4 Ti3Se4 v3s4
Cr,Se,
a
HCl, 400°C HC1, 4 0 0 T Electrochemical I,/acetonitrile H20 AlCl, I,/acetonitrile 30% aqueous H 2 0 2
21 21 22 16 23 24, 25 26 27 28 27 29 30 31 32 33 34 35
lT, octahedral
Solvated phases are prepared directly by uptake of solvated cations from solutions (reaction pathway 7). When the restriction of solvent exclusion is given up, the choice of solvent is nearly free; the only conditions to be fulfilled by the chosen solvent are reduction stability and no self-intercalation at the reaction temperature (normally RT). This makes accessible intercalation of all metal cations forming stable solvent complexes. The reduction of the host can be carried out by chemical reducing agents or by electrointercalation’. In contrast to the electronic insulating clay minerals, the negative charge of the layers is not fixed; hence, the size and the packing of the intercalated solvent complexes could determine the extent of charge transfer and the extension of the homogeneity ranges. The packing density may be influenced by Coulomb interaction between the cations and the negatively charged host lattices, between the cations, screening effects of the conduction band and the solvents. The homogeneity ranges need not be identical with those of the unsolvated metal intercalation compounds. Maximum uptake of cations and the connected charge transfer to the host lattices is in general lower than in the case of the unsolvated phases. The solvated intercalation compounds are accessible to solvent and ion exchange reactions like the layered clay minerals (pathways 5 and 6)16. These can be used to
268
3.11 Formation of the NonstoichiometricSulfides, Selenides, and Tellurides 3.1 1.6 By Insertion Reactions from Solutions
intercalate more complex species that cannot be intercalated directly because of their size. To achieve complete exchange of solvents or ions, these need multiple changes of the exchanging solutions and quantitative studies of the ion exchange capacity. Because of the advantages of the direct intercalation, these reaction pathways are not investigated to the same extent as with the layered alumosilicates. Some solvated phases of layered and chainlike host lattices can be solvated to such an extent that colloid solutions are formed (pathway 8)36. This so-called exfoliation is possible only if the charge on the host structure is very low. Mechanical forces can be applied to improve the dissolution. Reversal of this reaction, flocculation (pathway 9), is used to prepare new intercalation compounds not otherwise a c ~ e s s i b l e ~ ~ . The electrochemical intercalation in some semiconducting host lattices is supported by light3’. In all reactions discussed above it is tactily assumed that the structure of the host lattice remains unaffected. Neglecting changes in the layer stacking, this is the case for most of the host lattices and intercalates studied up to now. Recently it has been detected that the uptake of intercalate can induce a change of coordination (e.g., from MoS2 to Cd12 type)38.In addition, there are examples in which metal atoms of the structure building units are involved in the intercalation process (e.g., MPX3,LiFeS2, KCu4S3;see 3.11.6). The kinetics and mechanism of intercalation reactions have found increasing interest in recent y e a r ~ ~ ’ - ~Itl .is not quite clear how the results obtained by the different techniques applied to various intercalation compounds form a general scheme of reaction processes. (A. LERF) 1. N. Wiberg, ed., Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, founded by A. F.
Holleman, continued by E. Wiberg, Walter de Gruyter, Berlin, 1985. J. Falbe, M. Regitz, eds., Rompp Chemie Lexikon, 9th ed., Thieme, Stuttgart, 1995. W. Rudorff, Angew. Chem., 71, 487 (1959). W. Rudorff, Adv. Inorg. Chem. Radiochem., I , 223 (1959). G. H. Hennig, Prog. Inorg. Chem., I , 125 (1959). J. Rouxel, in Comprehensive Supramolecular Chemistry, 10, Vol. 7, G. Alberti, T. Bein, eds., Pergamon Press, Oxford, 1996. 7. R. Schollhorn, Angew. Chem., 92, 1015 (1980). 8. M. Kamaratos, C. A. Papageorgopoulos, Solid State Commun., 61, 567 (1987). 9. C. A. Papageorgopoulos, W. Jaegermann, Surf: Sci., 338, 83 (1995). 10. H. E. Brauer, H. I. Starnberg, L. J. Hollenboom, H. P. Hughes, Surf: Sci., 333, 419 (1995). 11. M. Remskar, V. Marinkovic, A. Prodan, Z. Skraba, Surf: Sci.,324, L367 (1995). 12. C . Pettenkofer, W. Jaegermann, B. A. Parkinson, Surf: Sci., 251, 583 (1991). 13. R. Schollhorn, Inclusion Compounds, Vol. 1,J. L. Atwood, J. E. D. Davies, D. D. MacNicol, eds., Academic Press, London, 1984. 14. M. S . Whittingham, Prog. Solid State Chem., 12, 41 (1978). 15. J. Devynck, R. Messina, J. Pingarron, B. Tremillon, L. Trichet, J . Electrochem. Soc., 131, 2274 (1984). 16. R. Schollhorn, in Intercalation Chemistry, M. S . Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. 17. D. W. Murphy, C . Cros, F. J. DiSalvo, J. V. Waszszak, Inorg. Chem., 16, 3027 (1977). 18. H. G. Schwarz, Ph.D. thesis, Tubingen, 1954. 19. C. F. van Bruggen, R. J. Haange, G. A. Wiegers, D. K. G. DeBoer, Physica, 99B, 166 (1980). 20. F. Wypych, R. Schollhorn, J . Chem. Soc., Chem. Commun., 1386 (1992). 21. F. Wypych, K Sollmann, R. Schollhorn, Muter., Res. Bull., 27, 545 (1992). 22. H. Boller, K. Hiebl, J . Alloys Comp., 183, 438 (1992). 23. P. Gard, C. Sourisseau, G. Ouvrard, R. Brec, Solid State Ionics, 20, 231 (1986). 2. 3. 4. 5. 6.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals ~
24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41.
269
~
R. Schollhorn, A. Payer, Angew. Chem., Int. Ed Engl., 24, 67 (1985). S. Sinha, D. W. Murphy, Solid State lonics, 20, 81 (1986). R. Chevrel, M. Sergent, J. Prigent, Mater., Res. Bull., 9, 1487 (1974). R. Chevrel, M. Sergent, in Crystal Chemistry and Properties of Materials with Quasi-OneDimensional Structures, J. Rouxel, ed., Reidel, Dordrecht, 1986. M. Potel, P. Gougeon, R. Chevrel, M. Sergent, Rez;. Chim. Miner., 21, 509 (1984). J. M. Tarascon, D. W. Murphy, Phys. Rez;. B, 33, 2625 (1986). J. M. Tarascon, G. W. Hull, Mat. Mater. Bull., 21, 859 (1986). R. Schollhorn, W. Schramm, D. Fenske, Angew. Chem. lnt. Ed. Engl., 19, 492 (1980). W. Bensch, J. Koy, T. Braun, P. Hug, Solid State lonics, 74, 141 (1994). W. Bensch, J. Koy, Acta Crystallogr., Sect. C , 49, 1133 (1993). T. Ohtani, Y. Sano, K. Kodoma, S. Onoue, H. Nishihara, Mater. Res. Bull., 28, 501 (1993). A. Nemudry, R. Schollhorn, J . Chem. SOC.,Chem. Comm., 2617 (1994). A. J. Jacobson, in Comprehensine Supramolecular Chemistry, Vol. 7, G. Alberti, T. Bein eds., Pergamon Press, Oxford, 1996. H. Tributsch, Solid Stare lonics, 9,10, 41 (1983). M. A. Py, R. R. Haering, Can. J . Phys., 61, 76 (1983). W. R. McKinnon, R. R. Haering in Modern Aspects of Electrochemistry, Vol. 15, R. E. White, J. M. Bockris, B. E. Conway, eds., Plenum Press, New York, 1983. T. Butz, A. Lerf, Ber. Bunsenges., Phys. Chem., 90, 638 (1986). S. J. Price, J. S. 0. Evans, R. J. Francis, D. O’Hare, Adz;.Mater., 8, 582 (1996).
3.1 1.6.1 Layered Transition Metal Dichalcogenides
In these dichalcogenides a sheet of metal atoms is strongly bound to and sandwiched between two hexagonally packed layers of chalcogens. Depending on the stacking of both layers, the metals are coordinated octahedrally as in the case of TiSz or trigonal prismatic as in ~H-MOS,.These X-M-X slabs (X = chalcogen atoms, M = transition metal) are weakly bound to other slabs and are stacked in the crystallographic c direction in different ways, leading to different polytypes. Perspective views of some of these polytypes are shown in Figure 1. Layered dichalcogenides are formed mainly by the early transition elements of groups IVB-VB. (A. LERF)
3.11.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals
Alkali metal intercalation compounds are prepared from the elements (pathway 3, Scheme 1, 3.11.6) or by reaction of the alkali metals with the dichalcogenides at high temperatures.’ Other high temperature methods involve the preparation in sulfur-containing fused salts or the treatment of oxides in HzS; this is the only way to obtain the ternary alkali metal compounds with fixed stoichiometry AMXz (A = Li, Na, K; M = V, Cr)2-4. The most widely applied method is the intercalation from liquid ammonia2,’. It has drawbacks: NH3 can be intercalated itself in a series of layered dichalcogenides leading to N H i contamination of the A,MSz compounds (3.11.6.1.5and 3.11.7.1.6),and, sinceNH3 is a very polar solvent it will cointercalate with the metal atoms, probably influencing the extent of the homogeneity ranges of the products. Alternatively, the method allows preparation of compounds with high intercalate content. Perhaps the solvent can be expelled from the interlayer space if the charge transfer and the metal content increase to the maximum value. Care must be taken to avoid formation of amide by-products, which would contaminate the solid. One solvent for alkali metal/intercalation in TaS,, hexamethyl phosphoric triamide (HMPA) is carginogenic6.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals ~
24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41.
269
~
R. Schollhorn, A. Payer, Angew. Chem., Int. Ed Engl., 24, 67 (1985). S. Sinha, D. W. Murphy, Solid State lonics, 20, 81 (1986). R. Chevrel, M. Sergent, J. Prigent, Mater., Res. Bull., 9, 1487 (1974). R. Chevrel, M. Sergent, in Crystal Chemistry and Properties of Materials with Quasi-OneDimensional Structures, J. Rouxel, ed., Reidel, Dordrecht, 1986. M. Potel, P. Gougeon, R. Chevrel, M. Sergent, Rez;. Chim. Miner., 21, 509 (1984). J. M. Tarascon, D. W. Murphy, Phys. Rez;. B, 33, 2625 (1986). J. M. Tarascon, G. W. Hull, Mat. Mater. Bull., 21, 859 (1986). R. Schollhorn, W. Schramm, D. Fenske, Angew. Chem. lnt. Ed. Engl., 19, 492 (1980). W. Bensch, J. Koy, T. Braun, P. Hug, Solid State lonics, 74, 141 (1994). W. Bensch, J. Koy, Acta Crystallogr., Sect. C , 49, 1133 (1993). T. Ohtani, Y. Sano, K. Kodoma, S. Onoue, H. Nishihara, Mater. Res. Bull., 28, 501 (1993). A. Nemudry, R. Schollhorn, J . Chem. SOC.,Chem. Comm., 2617 (1994). A. J. Jacobson, in Comprehensine Supramolecular Chemistry, Vol. 7, G. Alberti, T. Bein eds., Pergamon Press, Oxford, 1996. H. Tributsch, Solid Stare lonics, 9,10, 41 (1983). M. A. Py, R. R. Haering, Can. J . Phys., 61, 76 (1983). W. R. McKinnon, R. R. Haering in Modern Aspects of Electrochemistry, Vol. 15, R. E. White, J. M. Bockris, B. E. Conway, eds., Plenum Press, New York, 1983. T. Butz, A. Lerf, Ber. Bunsenges., Phys. Chem., 90, 638 (1986). S. J. Price, J. S. 0. Evans, R. J. Francis, D. O’Hare, Adz;.Mater., 8, 582 (1996).
3.1 1.6.1 Layered Transition Metal Dichalcogenides
In these dichalcogenides a sheet of metal atoms is strongly bound to and sandwiched between two hexagonally packed layers of chalcogens. Depending on the stacking of both layers, the metals are coordinated octahedrally as in the case of TiSz or trigonal prismatic as in ~H-MOS,.These X-M-X slabs (X = chalcogen atoms, M = transition metal) are weakly bound to other slabs and are stacked in the crystallographic c direction in different ways, leading to different polytypes. Perspective views of some of these polytypes are shown in Figure 1. Layered dichalcogenides are formed mainly by the early transition elements of groups IVB-VB. (A. LERF)
3.11.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals
Alkali metal intercalation compounds are prepared from the elements (pathway 3, Scheme 1, 3.11.6) or by reaction of the alkali metals with the dichalcogenides at high temperatures.’ Other high temperature methods involve the preparation in sulfur-containing fused salts or the treatment of oxides in HzS; this is the only way to obtain the ternary alkali metal compounds with fixed stoichiometry AMXz (A = Li, Na, K; M = V, Cr)2-4. The most widely applied method is the intercalation from liquid ammonia2,’. It has drawbacks: NH3 can be intercalated itself in a series of layered dichalcogenides leading to N H i contamination of the A,MSz compounds (3.11.6.1.5and 3.11.7.1.6),and, sinceNH3 is a very polar solvent it will cointercalate with the metal atoms, probably influencing the extent of the homogeneity ranges of the products. Alternatively, the method allows preparation of compounds with high intercalate content. Perhaps the solvent can be expelled from the interlayer space if the charge transfer and the metal content increase to the maximum value. Care must be taken to avoid formation of amide by-products, which would contaminate the solid. One solvent for alkali metal/intercalation in TaS,, hexamethyl phosphoric triamide (HMPA) is carginogenic6.
N
0
2Ha 2Hc
6R
s octhedralhole
o tetragonalhole (b)
rn trigonal prismatic hole
Figure 1. (a) Perspective views (1 120 sections through the unit cell) of some polymorphs and polytypes of MX, compounds. Large open circles correspond to the chalcogen atoms, small black dots correspond to the metal atoms. Capital letters assign the positions of the densely packed chalcogen layers; the metal layers are designated in lowercase. (b) Possible lattice sites for intercalated atoms: left octahedral and tetrahedral sites (there are twice as many tctrahedral as octahedral positions); right, possible trigonal prismatic sites (in general, only one of the positions can be occupied).
1T
3.1 1.6 By Insertion Reactions from Solutions 3.11.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals
27 1
Li intercalation compounds are obtained mainly by reaction with BuLi7. This reaction gives clean products with maximum Li uptake; samples of Li,MX2 are obtained after interruption of the reaction and long equilibration times. Other organometallics like sodium naphthalide have been used8. Chemical reduction occurs when LiBH4 is used; the reducing anion can be combined with other cations like Na, K, or NR:'. Reduction of the dichalcogenides by H2S occurs in alkali halide melts"; this method allows syntheses of the alkali metal intercalation compounds. The electrochemical method of intercalation is used widely to determine diffusion coefficients of the intercalated species in the different host lattices and to search for battery applications", ". Intercalation of unsolvated ions is possible only from solutions of their salts with anions like [AsF,]-, [PF,]-, or [C104]- in nonaqueous solvents like MeCN, dimethylcarbonate, ethylenecarbonate, or t e t r a h y d r o f ~ r a n ' ~ ~Details ' ~ . of electrochemical intercalation reactions of unsolvated ions are described3,"- 15. Comparison of the different preparation methods of alkali metal intercalation compounds has been described '. The most thoroughly studied systems are the Li intercalation compounds of most of the dichalcogenides' and the alkali metal (Li, Na, K, Rb, Cs) intercalation compounds of TiS22-4, ZrS22-4, and MoS2'*. Li and Na intercalation compounds of the tellurides (VTe,", NbTe220,21,TaTe," have been prepared recently by the BuLi method and by electrointercalation. The Li compounds have the most extended homogeneity ranges, reaching from x 0.3 up to x = 1. Only Li, TiS2 takes up Li homogeneously in the whole range 0 <x < 1. In the other compounds studied there is a sequence of 4th, 2nd, and 1st stage phases (this means intercalation in each 4th, 2nd, and in all interlayer galleries). The homogeneity ranges of the higher stage phases are very narrow. Packing density of the metals in the occupied interlayer galleries of the different stage phases is roughly identical to the lower limit of the homogeneity range of the 1st stage phase. Only the latter exhibits a broader homogeneity range, sometimes up to x 1. Some times the homogeneity range of the 1st-stage phase is divided in two smaller ones separated by a two-phase region; this is the case if a change in alkali metal coordination occurs with increasing metal content x (see e g , Na,TiS2). The homogeneity ranges differ slightly depending on the mode of preparation". Li prefers always octahedral coordination, whereas Rb and Cs occupy trigonal prismatic sites that are obtained only by a change in stacking of the MX2 layers. Coordination of Na and K depends on the dichalcogenide and the stoichiometry: eg., K is in trigonal-prismatic sites in TiS2 and Na is trigonal-prismatically coordinated for x<0.68 and octahedrally coordinated for 0.78<x < 12," (see Fig. 1). In ZrS, Na occupies octahedral sites, and K is the boundary between the structures with trigonalprismatic and octahedral coordination'. For particular compositions (x = 0.25, 0.33, or 0.5),ionic repulsion should lead to an ordering between occupied and empty sites, at least at sufficiently low temperatures. The tendency to order increases with the size of the ions and the ionicity of the host lattice. Ordered structures have been observed in Li, TiS2 and NaxTiS223. -4317
-
-
(i) Structural Transformations. Intercalation of alkali metals (and other intercalates) is often accompanied by a sliding of the MX2 slabs, leading to different layer stackings (polytype formation, change of the coordination of the guest species); however, the host layers are not modified. Such processes were described during the early stages of intercalation ~hemistry'~'~. Recently it has been detected that electron transfer during
272
3.11.6 By Insertion Reactions from Solutions 3.11.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals 4, 4,
0 akalirnetatal
M (Sn, Pb, In, TI)
lo
lo
81
01
Figure 1. 1120 sections for some selected intercalation compounds showing different patterns of layer intercalate arrangements. (a) Two different layer stackings and intercalate (sodium) positions for Na, Ti&. (b) One of the structural polymorphs for intercalation compounds of posttransition metals showing linear coordination of the intercalated metal. (c) Polymorph of Ag,TaS2.
intercalation of Li in MoS, can induce a change in Mo coordination from trigonal-prismatic to octahedral (1T The same transition has been observed in the case of K , M o S ~ ~This ~ . compound has been used to prepare the metastable 1T-MoS, (See Table 1,3.11.6).The reversal, a transition from octahedral coordination of the Ta metals in 1T-TaS, to the trigonal-prismatic one of 2H-TaS2 is induced by intercalation of Li and Na up to the maximum intercalate content of x = 1 and x = 0.8, respectively”. A much stronger structural transformation to a spinel structure has been observed for LiZrSz2’. (ii) Nonstoichiometry and Intercalation. Some dichalcogenides tend to deviate in stoichiometry from the ideal 1 :2 ratio. This deviation can result from an excess of metal between the layers (MI +,X2) or from chalcogen vacancies (MX2-,). The influence of nonstoichiometry on intercalation varies strongly with the type of defect, the nonstoichiometric dichalcogenide studied, and the temperature of intercalation. Thus, in HfTe2 -y the excess electrons due to Te vacancies remain localized near the vacancies whereas the electrons from intercalated lithium ions are transferred to the conduction band. The physical and structural changes are influenced mainly by the intercalate; the
3.11.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.1 Unsolvated Metal Intercalation Compounds: Alkali Metals
273
intercalation appears to be nearly unaffected by the deviation of stoi~hiometry~’.In nonstoichiometric ZrSe2-, it has been suggested that up to a Li content of x = 0.15 intercalation starts with occupancy of preferential sites bound to the vacancies created by stoichiometric deviation. This seems to be indicated by the absence of lattice expansion due to intercalation up to x = 0.1530. Excess metal atoms are expected to link the chalcogenide layers together so that Li diffusion is reduced in the interlayer gallery. In case of nonstoichiometric Til + *S2 excess metals reduce the self-diffusion coefficient of lithium but do not strongly influence the chemical diffusivity31.This is valid for excess metal content up to x = 0.13. High temperature formation of nonstoichiometric intercalation compounds leads to ordering of excess host metal atoms and the intercalate ions: e.g., in Na0.34Cr1.15Se2the extra Cr atoms (octahedral sites) and the Na atoms (trigonalprismatic sites) are located in alternating sequence in the interlayer galleries of the CrSe2 layers3’. (A. LERF)
1. W. P. F. A. M. Omloo, F. Jellinek, J . Less-Common Met., 20, 121, (1970). 2. J. Rouxel, in Intercalated Layered Materials, F. Levy, ed., Reidel Publishing Company, Dordrecht, 1979. 3. J. Rouxel, in Inorganic Reactions and Methods, Vol. 17, A. P. Hagen, ed., Verlag Chemie, New York, 1990. 4. R. Rouxel, in Comprehensive Supramolecular Chemistry, Vol. 7, G. Alberti, T. Bein, eds., Pergamon Press, Oxford, 1996. 5. W. Riidorff, Angew. Chem., 71, 487 (1959); Chimia, 19, 489 (1965). 6 . Y. Kanzaki, M. Konuma, A. Yamada, 0. Matsumoto, J. Phys. Chem. Solids, 40, 911 (1979). 7. M. B. Dines, Muter. Res. Bull., 10, 287 (1975). 8. E. Bayer, W. Rudorff, Z. Naturforsch. Teil B, 27, 1336 (1972). 9. M. G. Kanatzidis, T. J. Marks, Inorg. Chem., 26, 783 (1987). 10. R. Schollhorn, A. Lerf, J . Less Common Met., 42, 89 (1975). 11. W. B. Johnson, W. L. Worrell, Synth. Met., 4, 225 (1982). 12. M. S. Whittingham and A. J. Jacobson, eds., Intercalation Chemistry, Academic Press, New York, 1982. 13. J. 0. Besenhard, G. Eichinger, J . Electroanal. Chem., 68, 1 (1976). 14. G. Eichinger, J. 0. Besenhard, J. Electroanal. Chem., 72, 1 (1976). 15. M. S. Whittingham, Progr. Solid State Chem., 12, 41 (1978). 16. D. W. Murphy, S. A. Sunshine, S. M. Zahurak, in Chemical Physics of Intercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B 172, Plenum Press, New York, 1987. 17. H. Friend, A. D. Yoffe, Adv. Phys., 36, 1 (1987). 18. R. B. Somoano, J. A. Woolam, in Intercalated Layered Materials, F. Levy, ed., Reidel, Dordrecht, 1979. 19. R. Guzman, J. Morales, J. L. Tirado, Inorg. Chem., 33, 3164 (1994). 20. R. Guzman, J. Morales, J. L. Tirado, Chem. Muter., 7, 1171 (1995). 21. R. Guzman, J. Morales, J. L. Tirado, J . Muter. Chem., 3, 1271 (1993). 22. M.-H. Whangbo, J. Rouxel, L. Trichet, Inorg. Chem., 24, 1824 (1984). 23. T. Hibma, Physica B, 99, 136 (1980); J. Solid State Chem., 34, 97 (1980). 24. E. Sandre, R. Brec, J. Rouxel, J . Solid State Chem., 88, 269 (1990). 25. M. A. Py, R. R. Haering, Can. J . Phys., 61, 76 (1983). 26. W. J. Liang, in Condensed Systems of Low Dimensionality, J. L. Beeby, ed., NATO AS1 Series B 253, Plenum Press, New York, 1991. 27. P. Ganal, W. Olberding, T. Butz, G. Ouvrard, Solid State Ionics, 59, 313 (1993). 28. P. Deniard, P. Chevalier, L. Trichet, J. Rouxel, Synth. Met., 5, 14 (1983). 29. D. T. Hodul, A. M. Stacy, J . Phys. Chem. Solids, 46, 1447 (1985). 30. P. Deniard, P. Chevalier, L. Trichet, Y. Chabre, J. Pannetier, Solid State Commun., 64, 175 (1987). 31. T. Yamamoto, S. Kikkawa, M. Koizumi, Solid State Ionics, 17, 63 (1985). 32. D. Teigchelaar, R. J. Haange, G. A. Wiegers, C. F. van Bruggen, Muter. Res. Bull., 16,729 (1981).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
274 3.11.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.2 Unsolvated Metal Intercalation Compounds: Posttransition Metals 3.11.6.1.2 Unsolvated Metal Intercalation Compounds: Posttransition Metals
As is done elsewhere’, we shall count transition metals with a filled d shell Cu, Ag, Hg, etc.) as posttransition metals. This is justified because the intercalation compounds of these groups IB metals have some features in common with the intercalation compounds of the metals of groups IIIA-VA’. (i) Intercalation of Group IllA and VA Metals. Intercalation compounds of these metals appear in three different classes distinguished by stoichiometry and structure’. In compounds A0.33MX2(A = Sn, Pb, Bi; M = Nb, Ta; X = S, Se) the A atoms occupy octahedral interlayer positions. In A - O.&iX2 (A = In, T1: 0.5 < x < 0.9) the MX2 layers are shifted so that the sulfur layers of adjacent MX2 slabs are on top of each other. This leads to trigonal-prismatic holes occupied statistically by the A atoms. In the third group (AMX2with A = Ga, In, Sn, Pb, Bi; x < 1) the position of the adjacent MX2 layers is similar to that in the second group but the metals are coordinated linearly (one structure type, see 3.11.6.1, Fig. l), leading to a layer expansion of about 2.7& higher than in the other two groups. These phases are superconductors (Tc 3 K), and it is assumed that a conduction band of the intercalate has been formed’s3. These compounds are prepared by direct exposure of the dichalcogenides to the metal vapor or by heating the constituents in form of the elements (see 3.11.6, Scheme 1, pathway 3) or the corresponding chalcogenides’s2. The intercalation starts at temperatures well below the normal preparation temperatures4. Under these conditions metastable intermediate phases with narrow homogeneity ranges appear which are stable up to fairly high temperatures. For the In-TaS,, system a continuous decrease of an averaged valence has been observed when x increases from ca. 0.33 towards ca. 1. At the highest stoichiometries observed, a formal valence state of 1 has been obtained for G a and In and 0.66 for the Sn and Cd intercalates, suggesting formation of an intercalate conduction band in the latter two cases. Intercalation of In can be achieved also at RT by applying liquid In alloys (In-Ga eutectic or In amalgam) as the reaction medium. In both cases the intercalate phase is InTaS, with only a slight contamination of Ga and Hg5s6. InTaSz shows a phase transition at about 550K, accompanied by a change in charge transfer from 0.38 to 0.7 e-/TaS2, a change in the In coordination from linear to trigonal-prismatic, and a weakening of In-In bonds5% ‘.
-
(ii) Intercalation Compounds of Mercury. The gradual uptake of Hg at RT into TiS2 has been observed7. The most striking phenomenon of this new compound is the “superstoichiometric” uptake of Hg; the maximum stoichiometry amounts to x = 1.248. Reinvestigation of the Hg,TaSz system shows that the maximum content of Hg is x 1.39 if the insertion reaction is carried out at RT. This phase is stable only in the presence of excess Hg. The intercalated Hg forms hexagonal-close-packed monolayers in the interlayer galleries, which are incommensurate with the TaSz lattice”. There is a second phase Hgl,19TaSz’o, which shows a close structural relationship to Hg,,,,TiSZ8. In both compounds the Hg sublattice is an ordered array of infinite Hg chains, whose periodicity is incommensurate with that of the MS2 host lattice. A reversible thermal transition in Hg1.24TiS211at 468 K is associated with two-dimensional melting of the mercury sublattice.
-
(iii) Intercalation Compounds of Silver and Copper. Since these ions are highly mobile at RT, their insertion into the interlayer galleries of group IVB and VB dichalcogenides can be carried out not only at high temperature’, but also by means of
3.1 1.6 By Insertion Reactions from Solutions 275 3.11.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.2 Unsolvated Metal Intercalation Compounds: Posttransition Metals
electrochemical intercalation from aqueous or nonaqueous solutions16: e.g., AgxTaS212%13, AgxNbS214, or Cu,TaS215. AgxTiS212s13 (at high temperatures also”), and CuxTiXz’*~ have first been prepared by electrointercalation. In the Ag/MS2 systems three different phases with narrow homogeneity ranges exist. The first for x < 0.1 is called the “dilute gas phase” and contains randomly distributed Ag ions in all interlayer galleries, but this phase does not appear regularly in the electrointercalated samples. The homogeneity range of the second phase is centered around x = 0.2 for TiS2, x = 0.25 for NbS2, and x = 0.27 for TaSz; this phase is a second-stage phase (6R polytype in case of the latter two dichalcogenides (see 3.11.6.1.1, Fig. 1). The third phase is a first-stage compound with an Ag content about twice as high as in the second-stage phase. Since in the second phase only each second interlayer gap is occupied by Ag+ ions, the packing density in the occupied interlayer gaps is as high as in the first-stage phase. Whereas Ag in Ag,TiS2 is octahedrally coordinated, it occupies the tetrahedral sites in the groups VB dichalcogenides. With Ag,TaS2 the homogeneity ranges of the second and first-stage phases, transitions from the octahedral to the tetrahedral coordination of the Ag ions occur13.A kinetic study by monitoring nuclear quadrupole interaction (NQI) shows that the situation is far more complicated2’. At low x values two second-stage phases are formed simultaneously, the first one with octahedrally coordinated Ag, the second with tetrahedrally coordinated Ag; The onset of the first-stage phase is postponed until the second-stage phase has reached a maximum packing density, and it is accompanied with a temporary drop of the charge transfer and the appearance of a high NQI frequency component. These effects are correlated with the shear transformation from the 2H-TaSz to the 2H-MoS2 structure. In some of the Ag’6,21sz2compounds and in C U T ~ S , an , ~ ion ordering is observed near or slightly below RT. In Ag,TaS, very complex superstructures occur which can be described as a superposition of superlattices due to Agt ion ordering and those caused by an Agt ion-induced charge-density wave3,24. Two interesting phenomena observed in copper intercalation compounds should be noticed: CuXTiSz1’and CuxVX2 (X = S, Se)” undergo phase transition to the copper thiospinels when heated to about 4 0 0 T (see 3.11.6.4.2).Thermal decomposition of 2HCU~.~~M (MS=, Nb, Ta) results in the formation of ~ R - C U ~ . ~ in~ which M ~ +the~ S ~ excess M atoms and the Cu atoms are separated in alternating interlayer gaps (M atoms in octahedral and Cu in tetrahedral interstitial sites25.The Cu atoms can be removed by oxidation with iodine/MeCN forming a new modification of nonstoichiometric Tal +xSz accessible to intercalation in every second interlayer space26 (cf. Nao,34Crl.15Sezin 3.11.6.1.2).
’’
(A. LERF)
1. G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials, F. Levy, ed., Reidel, Dordrecht, 1979. 2. R. Eppinga, G. A. Wiegers, Physica B, 99, 121 (1980). 3. R. H. Friend, G. D. Yoffe, Adv. Phys., 36, 1 (1987). 4. T. Butz, U. Klapp, A. Lerf, in Chemical Physics oflntercalation, A. P. Legrand, S. Flandrois, ed., NATO AS1 Series B 172, Plenum Press, New York, 1987. 5. W. Olberding, T. Butz, A. Lerf, J. 0. Besenhard, Muter. Sci. Forum, 91-93, 427 (1992). 6. W. Olberding, P. Ganal, G. Ouvrard, T. Butz, Mol. Cryst. Liquid. Cryst. 244, 179 (1994). 7. E. W. Ong, M. J. McKelvy, W. S. Glaunsinger, Chem. Muter., 4, 14 (1992). 8. P. Moreau, P. Ganal, G. Ouvrard, M. Sidorov, M. McKelvy, W. Glaunsinger, Chem. Muter., 7, 1132 (1995). 9. P. Ganal, W. Olberding, T. Butz, G. Ouvrard, in Chemical Physics oflntercalation ZI, P. Bernier, J. E. Fischer, S. Roth, S. A. Solin, eds., NATO AS1 Series B 305, Plenum Press, New York, 1993.
276
3.11.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.3 Unsolvated Metal Intercalation Compounds: Transition Metals
10. P. Ganal, P. Moreau, G. Ouvrard, W. Olberding, T. Butz, Phys. Rev. B, 52, 11359 (1995). 11. P. Ganal, P. Moreau, S. Lemaux, G. Ouvrard, M. McKelvy, J . Phys. Chem. Solids, 57, 1129 (1996). 12. G. A. Scholz, R. F. Frindt, Muter. Res. Bull., 15, 1703 (1980). 13. G. A. Scholz, R. F. Frindt, J . Electrochem. Soc. 131, 1763 (1984). 14. H. J. Bouwmeester, Solid State Ionics, 16, 163 (1985). 15. C. Ramos, A. Lerf, T. Butz, Hypery’ine Interactions, 61, 1209 (1990). 16. A. G. Gerards, H. Roede, R. J. Haange, B. A. Boukamp, G. A. Wiegers, Synth. Met., 10, 51 (1984/85). 17. R. Schollhorn, in Inclusion Compounds, Vol. 1, J. L. Atwood, J. E. D. Davies, D. D. MacNieal, eds., Academic Press, London, 1984. 18. R. Schollhorn, in Physics of Intercalation Compounds, Vol. 38, Springer Series in Solid-state Sciences, L. Pietronero, E. Tosatti, eds., Springer-Verlag,Berlin, 1981. 19. R. Schollhorn,in Chemical Physics oflntercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B, 172, Plenum Press, New York, 1987. 20. C. Ramos, A. Lerf, T. Butz, Ber. Bunsenges, Phys. Chem., 93, 1209 (1989). 21. J. Mahy, G. A. Wiegers, F. van Bolhuis, A. Diedering, R. J. Haange, Phys. Status Solidi, A , 107, 873 (1988). 22. G . A. Wiegers, R. J. Haange, F. van Bolhuis, Phys. Status Solidi, A , 107, 817 (1988). 23. R. DeRidder, G. van Tendeloo, J. van Landuyt, D. van Dyck, S. Amelinckx, Phys. Status Solidi, A , 37, 591 (1976). 24. G. A. Scholz, R. F. Frindt, A. E. Curzon, Phys. Status Solidi. A , 71,531 (1982);Phvs. Status Solidi, A , 72, 375 (1982). 25. B. Harbrecht, G. Kreiner, Z . Anorg. Allg. Chem. 572, 47, (1989). 26. K. Bohnen, Ph.D. Thesis, Bonn, Germany, 1995.
3.1 1.6.1.3 Unsolvated Metal Intercalation Compounds: Transition Metals
Transition metal intercalation compounds have been studied for their electrical and magnetic p r ~ p e r t i e s l - ~With . the exception of Rh (in TaS2 and NbSe,) only 3d elements have been inserted into the dichalcogenides; Fe, Co, and Ni derivatives of TiS,, ZrS,, ZrSe2 (Fe only), NbS,, NbSe,, TaS2, and TaSe,, are known. Insertion of Ti, V, Cr, and M n is restricted to the group VB dichalcogenides NbS2, NbSe,, TaS2, and TaSez. Metal atoms occupy octahedral lattice sites. These compounds are prepared at high temperatures (see Scheme 1, pathway 3, in 3.1 1.6) or by intercalation of the pure element at temperatures higher than 700°C. Crystal growth via vapor phase transport has been observed2s3. These compounds are more properly considered as interstitial compounds. Low mobility results in ordering of the intercalated species. Superstructures parallel to the layer planes are observed. There is a 2a x 2a superstructure in compounds with the stoichiometry x = 1/4 and a a x a$ supercell for x = 1/3. Despite these superstructures, the homogeneity range of these phases can be much broader, e.g., for the group VB dichalcogenides x varies in the limits 0.1-0.2 < x < 0.5. For the dichalcogenides the homogeneity range can be much broader: the lower limit is near x = 0, and the upper limit depends on the intercalation temperature and the metal inserted2,
’.
(A. LERF)
R. H. Friend, A. D. Yoffe, Adu. Phys., 36, l(1987). G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials, F. Levy, ed., Reidel, Dordrecht, 1979. A. R. Beal, in Chemical Physics of Intercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B 172, Plenum Press, New York, 1987. S. S. P. Parkin, R. H. Friend, Philos. Mag., 41, 65, (1980); 41, 95 (1980).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
276
3.11.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.3 Unsolvated Metal Intercalation Compounds: Transition Metals
10. P. Ganal, P. Moreau, G. Ouvrard, W. Olberding, T. Butz, Phys. Rev. B, 52, 11359 (1995). 11. P. Ganal, P. Moreau, S. Lemaux, G. Ouvrard, M. McKelvy, J . Phys. Chem. Solids, 57, 1129 (1996). 12. G. A. Scholz, R. F. Frindt, Muter. Res. Bull., 15, 1703 (1980). 13. G. A. Scholz, R. F. Frindt, J . Electrochem. Soc. 131, 1763 (1984). 14. H. J. Bouwmeester, Solid State Ionics, 16, 163 (1985). 15. C. Ramos, A. Lerf, T. Butz, Hypery’ine Interactions, 61, 1209 (1990). 16. A. G. Gerards, H. Roede, R. J. Haange, B. A. Boukamp, G. A. Wiegers, Synth. Met., 10, 51 (1984/85). 17. R. Schollhorn, in Inclusion Compounds, Vol. 1, J. L. Atwood, J. E. D. Davies, D. D. MacNieal, eds., Academic Press, London, 1984. 18. R. Schollhorn, in Physics of Intercalation Compounds, Vol. 38, Springer Series in Solid-state Sciences, L. Pietronero, E. Tosatti, eds., Springer-Verlag,Berlin, 1981. 19. R. Schollhorn,in Chemical Physics oflntercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B, 172, Plenum Press, New York, 1987. 20. C. Ramos, A. Lerf, T. Butz, Ber. Bunsenges, Phys. Chem., 93, 1209 (1989). 21. J. Mahy, G. A. Wiegers, F. van Bolhuis, A. Diedering, R. J. Haange, Phys. Status Solidi, A , 107, 873 (1988). 22. G . A. Wiegers, R. J. Haange, F. van Bolhuis, Phys. Status Solidi, A , 107, 817 (1988). 23. R. DeRidder, G. van Tendeloo, J. van Landuyt, D. van Dyck, S. Amelinckx, Phys. Status Solidi, A , 37, 591 (1976). 24. G. A. Scholz, R. F. Frindt, A. E. Curzon, Phys. Status Solidi. A , 71,531 (1982);Phvs. Status Solidi, A , 72, 375 (1982). 25. B. Harbrecht, G. Kreiner, Z . Anorg. Allg. Chem. 572, 47, (1989). 26. K. Bohnen, Ph.D. Thesis, Bonn, Germany, 1995.
3.1 1.6.1.3 Unsolvated Metal Intercalation Compounds: Transition Metals
Transition metal intercalation compounds have been studied for their electrical and magnetic p r ~ p e r t i e s l - ~With . the exception of Rh (in TaS2 and NbSe,) only 3d elements have been inserted into the dichalcogenides; Fe, Co, and Ni derivatives of TiS,, ZrS,, ZrSe2 (Fe only), NbS,, NbSe,, TaS2, and TaSe,, are known. Insertion of Ti, V, Cr, and M n is restricted to the group VB dichalcogenides NbS2, NbSe,, TaS2, and TaSez. Metal atoms occupy octahedral lattice sites. These compounds are prepared at high temperatures (see Scheme 1, pathway 3, in 3.1 1.6) or by intercalation of the pure element at temperatures higher than 700°C. Crystal growth via vapor phase transport has been observed2s3. These compounds are more properly considered as interstitial compounds. Low mobility results in ordering of the intercalated species. Superstructures parallel to the layer planes are observed. There is a 2a x 2a superstructure in compounds with the stoichiometry x = 1/4 and a a x a$ supercell for x = 1/3. Despite these superstructures, the homogeneity range of these phases can be much broader, e.g., for the group VB dichalcogenides x varies in the limits 0.1-0.2 < x < 0.5. For the dichalcogenides the homogeneity range can be much broader: the lower limit is near x = 0, and the upper limit depends on the intercalation temperature and the metal inserted2,
’.
(A. LERF)
R. H. Friend, A. D. Yoffe, Adu. Phys., 36, l(1987). G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials, F. Levy, ed., Reidel, Dordrecht, 1979. A. R. Beal, in Chemical Physics of Intercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B 172, Plenum Press, New York, 1987. S. S. P. Parkin, R. H. Friend, Philos. Mag., 41, 65, (1980); 41, 95 (1980).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.4 “Misfit Layer Compounds”
277
3.11.6.1.4 “Misfit Layer Compounds”
“Misfit layer structures” consist of at least two more or less independent layers for which one or two intralayer periodicities do not coincide. A broader range of synthetic composite compounds exhibiting such a structural type has been obtained recently in the field of chalcogenide chemistry’-3. The building principle of these “misfit layer compounds” consists of an alternating stacking sequence of two layered arrangements (AX and MXz)giving a composite arrangement of the formula (AX), +x(MXz)m with A = Sn, Pb, Bi, Sb, rare earths; M = Ti, V, Cr, Nb, Ta; X = S, Se; 0.08 < x < 0.28; m = 1-3. Each set of layers possesses its own symmetry and unit cell constant parameters. Incommensurate behavior arises from the noncoincidence of periodicities between the two component layers, along at least one crystallographic direction. Most compounds studied are incommensurate along the a crystallographic direction; periodicities along b and c are identical or multiples of each other, and c is chosen as the stacking direction. The AX part of the composite consists of a two-atom-thick layer with a distorted NaCl structure. The structure of the MX2 part is identical with the structure of the corresponding dichalcogenide. The ratio of AX to (MX,), is determined by the perodicity ratios a,(AX) and a2 (MX,) of the two subsystems, expressed by the variable x = (4/2) (az/al)- 1; the factor 4/2’is due to the number of formula units per slab (4 for AX and 2 for MXz). The m value is the ratio between the number of MX2 and AX entities along the stacking direction. Since the structural determination of composite compounds can be derived from a separate treatment of each constituent, and since a parallel can be established between the electrical properties of misfit layer compounds and the intercalated compounds AxMS2, one can formally consider the misfit compounds as intercalates of the MXz components, the intercalated species being the AX part. One can suppose a charge transfer from AX to MXZ4.The question of charge transfer is connected with the question of what stabilizes the structure of these complex composites. There is another interpretation, namely, that some additional M atoms are inserted in the AX units’. The misfit compounds were prepared by high temperature reactions of the elements in the ratio expected for a misfit layer compound. Crystal growth by vapor phase transport with Clz as the transport agent is possible. Lithium i n t e r c a l a t i ~ n ~(carried ~’ out at RT using the BuLi method) has been observed in several of these misfit structures. At prolonged treatment with BuLi, a complete amorphization takes places, which is partly reversible if the sample is delithiated. The Li content is lower in the 1 : 1 : 3 phase (m = 1; the numbers in the ratio indicate atoms in the formula: 1 Pb, 1 Ti, 3 S) than in the 1 : 2 : 5 phase (m = 2), which contains a sequence of successive MXz layers with a van der Waals gap between them. These latter phases allow the additional uptake of water molecules8 (demonstrated in (PbS), (TiS,),) or nalkylaminesg [in (PbS), (Ti&), and (PbS),(TaS,),] and exfoliation reactions”. The lithiated 1 : 1 : 3 compound Li0.65(PbS),(VSz)can take up in addition alkylamines”. The 3d transition metals Fe and Ni and the rare earth metals La and Ce have also been intercalated
’.
(A. LERF)
1. 2. 3. 4.
G. A. Wiegers, A. Meerschaut, Mater. Sci. Forum, 100-101, 1 (1992). A. Meerschaut, Curr. Opin. Solid State Mater. Sci., I , 250 (1996). G. A. Wiegers, Prog. Solid State Chem., 24, 1 (1996). J. Rouxel, A. Meerschaut, G. A. Wiegers, J . Alloys Cornpd., 229, 144 (1995).
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.5 Solvated Phases
278
Y. Moelo, A. Meerschaut, J. Rouxel, C . Auriel, Chem. Muter., 7, 1759 (1995). L. Hernan, P. Lavela, J. Morales, J. Pattanayak, J. L. Tirado, Muter. Res. Bull., 26, 1211 (1991). L. Hernan, J. Morales, J. Pattanayak, J. L. Tirado, J . Solid State Chem., 100, 262 (1992). P, Lavela, J. Morales, J. L. Tirado, Chem. Muter., 4 , 2 (1992). L, Hernan, P. Lavela, J. Morales, L. Sanchez, J. L. Tirado, J . Muter. Chem., 6, 861 (1996). 10. P. Bonneau, J. L. Mansot, J. Rouxel, Muter. Res. Bull., 28, 757 (1993). 11. R. Guzman, L. Hernan, J. Morales,J. Pattanayak, J. L. Tirado, Muter. Res. Bull., 28,469 (1993). 12. K. Suzuki, 0. Nakamura, T. Kondo, T. Enoki, J . Phys. Chem. Solids, 57, 1133 (1996). 5. 6. 7. 8. 9.
3.1 1.6.1.5 Solvated Phases
(i) Hydrated Systems. Alkali metal intercalation compounds absorb H2O forming the hydrated systems A , ( H ~ O ) , M X Z ' - ~The . hydration reaction can be accompanied by reduction of H z O and partial deintercalation of the cations. The process is finished when the electrochemical potential of the intercalation compound is reduced to the redox potential of H2O (pH dependent). This can be the case at very different x values e.g., it is at x 0.45 for Li,TaSz4 and x 0.1 for A,MoSz5. In some ternary compounds with fixed stoichiometry (e.g., KCrS, or KCrSe202)or other oxidizing agents must be applied to start the intercalation of water6. In mineral acids, complete deintercalation can occur4. Hydrated alkali cations can also be intercalated directly by applying reducing agents, like borohydrides or Na2Sz0d7. A special variant of this method is the intercalation of alkali metals from A O H solutions (for 2H-TaS2 and 2H-NbS2 only)8. The hydrolysis by OH releases S z - ions, which can act as a strong reducing agent at high pH7,9,10.Increasing the AOH concentration increases the charge transfer up to about 0.4 e-/TaS2. At still higher N a O H concentration, the supernatant solution N a O H is taken up in the interlayer gap'. The most elegant and widely applicable method is electrochemical intercalation. For preparative purposes a simple, three- or four-compartment glass cell, as shown schematically in Figure 1is sufficient. Most reliable results are obtained when crystals are used for intercalation; this gives the additional opportunity to monitor crystal expansion in situ by means of a dilatometer" (Fig. 2). This method was first used to intercalate hydrated alkali metal, alkaline earth metal, and some ammonium cations'2x'3. The only system studied in more detail is the potassium intercalation in 2H-TaS2. A single phase (first stage) exists in the region 0.21(0.27) ix < 0.4514,15(the value in parentheses is found for intercalation into crystals); the upper limit is determined by the H 2 0decomposition. Below x = 0.21 (0.27) there are two phase regions (Fig. 3). The intermediate phases are higher stage compounds whose packing density is identical to that of the lower limit of the first-stage phase. Using the electrochemical method, it is possible to intercalate nearly all cations forming stable hydrate complexes in HzO into crystals of 2H-TaSz: e.g., alkali cations, alkaline earth ions, transition metal ions (Fez+,M n Z + ,C o z c , Ni2+,Cr3f)143'6, and rare earth The intercalation compounds of the hydrated transition metal and rare earth metal ions can be obtained only this way. Surprisingly, the homogeneity range is nearly identical for all these hydrated ions. The lower limit is that of the potassium phase (x = 0.27); the upper limit is shifted to lower values (x 0.35) for the transition metal and rare earth ions because of the slightly acidic character of the metal hydrate complexes in aqueous solutions16. There are hydrated phases A,(HzO),MXZ of the sulfides of M = Ti, V, Nb, Ta (2H and 1T modifications), Cr, Mo, Sn"-". Hydrated phases of the selenides are rare (M = V, Cr). The M o and Sn compounds are very sensitive to complete deintercalation.
-
-
-
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.5 Solvated Phases
278
Y. Moelo, A. Meerschaut, J. Rouxel, C . Auriel, Chem. Muter., 7, 1759 (1995). L. Hernan, P. Lavela, J. Morales, J. Pattanayak, J. L. Tirado, Muter. Res. Bull., 26, 1211 (1991). L. Hernan, J. Morales, J. Pattanayak, J. L. Tirado, J . Solid State Chem., 100, 262 (1992). P, Lavela, J. Morales, J. L. Tirado, Chem. Muter., 4 , 2 (1992). L, Hernan, P. Lavela, J. Morales, L. Sanchez, J. L. Tirado, J . Muter. Chem., 6, 861 (1996). 10. P. Bonneau, J. L. Mansot, J. Rouxel, Muter. Res. Bull., 28, 757 (1993). 11. R. Guzman, L. Hernan, J. Morales,J. Pattanayak, J. L. Tirado, Muter. Res. Bull., 28,469 (1993). 12. K. Suzuki, 0. Nakamura, T. Kondo, T. Enoki, J . Phys. Chem. Solids, 57, 1133 (1996). 5. 6. 7. 8. 9.
3.1 1.6.1.5 Solvated Phases
(i) Hydrated Systems. Alkali metal intercalation compounds absorb H2O forming the hydrated systems A , ( H ~ O ) , M X Z ' - ~The . hydration reaction can be accompanied by reduction of H z O and partial deintercalation of the cations. The process is finished when the electrochemical potential of the intercalation compound is reduced to the redox potential of H2O (pH dependent). This can be the case at very different x values e.g., it is at x 0.45 for Li,TaSz4 and x 0.1 for A,MoSz5. In some ternary compounds with fixed stoichiometry (e.g., KCrS, or KCrSe202)or other oxidizing agents must be applied to start the intercalation of water6. In mineral acids, complete deintercalation can occur4. Hydrated alkali cations can also be intercalated directly by applying reducing agents, like borohydrides or Na2Sz0d7. A special variant of this method is the intercalation of alkali metals from A O H solutions (for 2H-TaS2 and 2H-NbS2 only)8. The hydrolysis by OH releases S z - ions, which can act as a strong reducing agent at high pH7,9,10.Increasing the AOH concentration increases the charge transfer up to about 0.4 e-/TaS2. At still higher N a O H concentration, the supernatant solution N a O H is taken up in the interlayer gap'. The most elegant and widely applicable method is electrochemical intercalation. For preparative purposes a simple, three- or four-compartment glass cell, as shown schematically in Figure 1is sufficient. Most reliable results are obtained when crystals are used for intercalation; this gives the additional opportunity to monitor crystal expansion in situ by means of a dilatometer" (Fig. 2). This method was first used to intercalate hydrated alkali metal, alkaline earth metal, and some ammonium cations'2x'3. The only system studied in more detail is the potassium intercalation in 2H-TaS2. A single phase (first stage) exists in the region 0.21(0.27) ix < 0.4514,15(the value in parentheses is found for intercalation into crystals); the upper limit is determined by the H 2 0decomposition. Below x = 0.21 (0.27) there are two phase regions (Fig. 3). The intermediate phases are higher stage compounds whose packing density is identical to that of the lower limit of the first-stage phase. Using the electrochemical method, it is possible to intercalate nearly all cations forming stable hydrate complexes in HzO into crystals of 2H-TaSz: e.g., alkali cations, alkaline earth ions, transition metal ions (Fez+,M n Z + ,C o z c , Ni2+,Cr3f)143'6, and rare earth The intercalation compounds of the hydrated transition metal and rare earth metal ions can be obtained only this way. Surprisingly, the homogeneity range is nearly identical for all these hydrated ions. The lower limit is that of the potassium phase (x = 0.27); the upper limit is shifted to lower values (x 0.35) for the transition metal and rare earth ions because of the slightly acidic character of the metal hydrate complexes in aqueous solutions16. There are hydrated phases A,(HzO),MXZ of the sulfides of M = Ti, V, Nb, Ta (2H and 1T modifications), Cr, Mo, Sn"-". Hydrated phases of the selenides are rare (M = V, Cr). The M o and Sn compounds are very sensitive to complete deintercalation.
-
-
-
3.11.6 By Insertion Reactions from Solutions 3.1 1.6.1 La ered Transition Metal Dichalcogenides 3.11.6.1.5 iolvated Phases
C
w
279
R
Figure 1. Schematic drawing of glass cell used for preparative electrointercalation experiments. The Schlenck ware modification allows working" under argon atmosphere. The central compartment is mounted by the sample holder (W); the other two by a Pt counter electrode (C) (in four-compartment cells, there are two counter electrodes) and the standard calomel reference electrode (R). The anodic and cathodic compartments are separated by glass diaphragms. Whenever possible, crystals are used for intercalation. The sample holder consists of a frame mounted with a fixed gold piston which serves as the sample and the electrical contact. The second piston is of Teflon or another non-swelling polymer as the frame. This piston is free to move and keeps the crystal on a fixed position on the gold support. Electrointercalation is under constant current conditions. Usually current on the order of a few microamperes applied, allowing the intercalation process to remain near equilibrium. The amount of H2O absorbed in the interlayer gaps depends on the metal ions; the spacing is about 12 for all divalent cations; for Li and Na, about 9 8, for the monovalent cations K, Rb, and CsZ1,and still larger than 12 A for the three-valent ions14,17 . Water content depends on the HzO vapor pressure surrounding the samples. The transition from the fully hydrated state (12 A; 2 water layers) to the partially dried state (1 water layer) occurs at about 50% relative humidity". In a very careful study of the hydration behavior of Na0,33(H2O),TaS2,four phases of different H 2 0 content could be observed, two of them with a well-ordered arrangement of HzO and sodium ionsz2. In case of the hydronium phases H,(H20),MS2(M = TaZ3, NbZ4) and the L ~ , ( H z O ) , M O S Zwith ~ ~ a very low cation content x 0.1, the swelling can go to the colloidal state under complete exfoliation of the crystals. By flocculation of the colloid, new intercalation compounds can be obtained, e.g., by preparation of transition metal and rare earth intercalation compounds AX(H20),MoS2 with A = Fe, Co, Ni, Y, La, Er, ThZ6.The preparation of unsolvated metal complexes with this method2' has been described also. (ii) Ammoniated Systems. Whereas many alkali metal intercalation compounds have been prepared in liquid NH3 solutions, only two NH3-containing solvate phases AX(NH3),TiS2(A = Li, Eu) have been studied r e ~ e n t l y ~ * -Samples ~'. must be kept under NH3 and under dry atmosphere to prevent NH3 loss and reaction with H2O. Up to a charge transfer n of 0.22, e-/TiSr metal and NH$ ions coexist. The latter originate from
280
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 Layered Transition Metal Dichalcogenides 3.1 1.6.1.5 Solvated Phases WORKING
ELECTRODE (Au)
J
Figure 2. Schematic drawing of the dilatometer used for monitoring crystal expansion. With layered crystals, the macroscopic crystal expansion can be determined during the electrointercalation (in situ). The recording of the crystal thickness is based on the resonance frequency shift of an oscillator circuit whose inductivity consists of a ferrite coil with a variable slit. The crystal is placed between two plane-parallel pistons. The lower piston consists of gold (for aqueous solutions) and serves as electrical contact. The upper piston consists of Teflon or epoxy and transmits the crystal expansion to the upper ferrite shell. This axis is supported by two springs. Within the ferrite shell there is a coil with inductivity 2 mH. This coil is part of an oscillator circuit whose frequency is changed by the distance between the two ferrite shells, and this distance changes with the thickness of the crystal. the NH3 self-intercalation, which is accompanied by the oxidation of NH3 (see 3.1 1.6.1.6). The content of both cations adds always to the sum of x + n = 0.22. In the Eu compound three cations can be found, Eu”, Eu3+,and NHZ; again the sum of the charge transfer of the three species adds to n = 0.22 (calculating the content of the metals consider the valence of the metal cations). (iii) Systems Containing Other Solvents. In the hydrated phases HzO can be replaced by other polar solvents’832’,3 1 . The polar solvents alcohol, dioles, ethers, acetamides, NMF, DMF, and DMSO, are known to replace HzO. There is no clear correlation between the solvent uptake capability of the solid and any parameters
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 La ered Transition Metal Dichalcogenides 3.1 1.6.1.5 .!&lvated Phases
-s
50
I
Intercalation
,
I
28 1
Dein t e r calat ion
4
1
\
J
a
25
0
02 0
w 0 m
2 3.0
> u w - 0.2 -0.L
0.125 0.152
Figure 3. Typical potential-charge transfer-crystal expansion curve for an intercalation/deintercalation cycle of hydrated potassium into 2H-TaS2 obtained applying the dilatometer shown in Figure 2. Crystal expansion is finished when the intercalate content reaches the lower limit of the homogeneity range. Within the homogeneity range of the first-stage phase x > 0.27, the electrochemical potential changes strongly, whereas the crystal expansion is nearly constant, thus the packing density of the intercalate increases. In regions x < 0.27 the potential curve is nearly horizontal, indicating two phase regions separated by steps in the potential curve and retardation of crystal expansion. This is accompanied by transition from the second-stage to the first-stage phase. Shape of the steps in the potential curve varies with preparation conditions of the crystals and is strongly correlated with steps in the crystals expansion.
characterizing the donor properties of the solvents. There is only a weak correlation with Gutmann’s donicity number DN; for cointercalation of the solvent, its DN number should be higher than 1LI3’. It is likely that residual H20 will be retained in the solid. This can be avoided if the intercalation is carried out electrochemically from the salt solutions in the solvent to be cointercalated with the cations. Few systems have been studied so far; the first was
282
3.1 1.6 By Insertion Reactions from Solutions 3.11.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.6 Molecular Intercalation Compounds
A , ( D M S O ) , M O S ~The ~ ~ . layer distance of the sodium compound is in the same order as for the DMSO exchanged compound’. The cation content of the first stage compound is x = 0.125 nearly independent of the cation. Such low intercalate contents have also been obsereved in the electrochemical intercalation of potassium in 2H-TaS2 from DMSO (x 0.1) and D M F (x 0.19) solution^^^*^^. These are much lower than the alkali content in the hydrated phases. Thus the size of the solvent complexes seems to influence the charge transfer to the host. The exfoliation of NaX(H20/NMF),TaS2in H’O/NMF mixtures to a stable colloidz1 could be caused by a charge transfer reduction, since Na0.33(H20y)TaS2does not exfoliate in HzO.
-
-
(A. LERF)
1. R. Schollhorn, A. Weiss, Z . Naturforsch. Teil B, 28, 711 (1973). 2. G. A. Wiegers, R. van der Meer, H. van Heiningen, Muter. Res. Bull., 9, 1261 (1974). 3. G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials. F. Levy, ed., Reidel, Dordrecht, 1979. 4. T. Butz, A. Lerf, J. 0. Besenhard, Rec. Chim. Miner., 21, 556 (1984). 5. R. Schollhorn, A. Weiss, J . Less-Common Met., 36, 229 (1974). 6. R. Schollhorn, R. Arndt, A. Kubny, J . Solid State Chem., 29, 259 (1979). 7. R. Schollhorn, E. Sick, A. Lerf, Muter. Res. Bull., 10, 1005 (1975). 8. F. R. Gamble, J. H. Osiecki, M. Cais, R. Pisharody, F. J. DiSalvo, T. H. Geballe, Science, 174, 493 (1971). 9. W. Biberacher, A. Lerf, F. Buheitl, T. Butz, A. Hubler, Muter. Res. Bull., 17, 633 (1982). 10. R. Schollhorn, in Chemical Physics of Intercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B, 172, Plenum Press, New York, 1987. 11. W. Biberacher, A. Lerf, J. 0.Besenhard, H. Mohwald,T. Butz, Muter. Res. Bull., 17, 1385 (1982). 12. R. Schollhorn, H. Meyer, Muter. Res. Bull., 9, 1237 (1974). 13. G. V. Subba Rao, J. C. Tsang, Muter. Res. Bull., 9, 921 (1974). 14. C. Riekel, H. G. Reznik, R. Schollhorn, J . Solid State Chem., 34, 253 (1980). 15. T. Butz, A. Lerf, Rev. Chim.Miner., 19, 496 (1982). 16. W. Biberacher, A. Lerf, J. 0. Besenhard, H. Mohwald, T. Butz, S. Saibene, Nuoao Cimento, 2D, 1706 (1983). 17. C. von Wesendonck, W. Biberacher, A. Lerf, Solid State Commun., 74, 183 (1989). 18. R. Schollhorn, Angew. Chern., 92, 1015 (1980). 19. R. Schollhorn, in Intercalation Chemistry, M . S. Whittingham, A. Jacobsen, eds., Academic Press, New York, 1982. 20. C. Ritter, R. Schollhorn, Solid State Comrnun., 61, 117 (1987). 21. A. Lerf, R. Schollhorn, Inorg. Chern., 16, 2950 (1977). 22. D. C. Johnston, J . Less-Common Met., 84, 327 (1982); Muter. Res. Bull., 17, 13 (1982). 23. D. W. Murphy, G. W. Hull, J . Chem. Phys., 62, 967 (1975). 24. C. Liu, 0. Singh, P. Joensen, A. E. Curzon, R. F. Frindt, Thin Solid Films, 113, 165 (1984). 25. P. Joensen, R. F. Frindt, S. R. Morrison, Muter. Res. Bull., 21, 457 (1986). 26. A. S. Golub, G. A. Protzenko, I. M. Yanovskaya, 0. L. Lependina, Y. N. Novikov, Mendel. Cornmun., 199 (1993). 27. M. A. Gee, R. F. Frindt, P. Joensen, S. R. Morrison, Muter. Res. Bull., 21, 543 (1986). 28. M. McKelvy, L. Bernard, W. Glaunsinger, P. Colombet, J . Solid State Chem., 65, 79 (1986). 29. S. P. Hsu. W. S. Glaunsinger, J . Solid State Chern., 67, 109 (1987). 30. P. Colombet, M. Danot, J. Rouxel, W. Glaunsinger, J . Less-Common Met., 156, 413 (1989). 31. M. S. Whittngham, Prog. Sol. State Chern., 12, 41 (1978). 32. A. Lerf, Habilitationsschrift, Munich, 1991. 33. J. 0. Besenhard, H. Meyer, R. Schollhorn, Z . Naturforsch., Teil B, 31, 907 (1976). 34. C. Ramos, Diploma thesis, Munich, 1986. 3.1 1.6.1.6 Molecular Intercalation Compounds
Intercalation of molecules into the layered dichalcogenides is known’. Discovery of superconductivity in some of these’ led to vigorous research activities in this field.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
282
3.1 1.6 By Insertion Reactions from Solutions 3.11.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.6 Molecular Intercalation Compounds
A , ( D M S O ) , M O S ~The ~ ~ . layer distance of the sodium compound is in the same order as for the DMSO exchanged compound’. The cation content of the first stage compound is x = 0.125 nearly independent of the cation. Such low intercalate contents have also been obsereved in the electrochemical intercalation of potassium in 2H-TaS2 from DMSO (x 0.1) and D M F (x 0.19) solution^^^*^^. These are much lower than the alkali content in the hydrated phases. Thus the size of the solvent complexes seems to influence the charge transfer to the host. The exfoliation of NaX(H20/NMF),TaS2in H’O/NMF mixtures to a stable colloidz1 could be caused by a charge transfer reduction, since Na0.33(H20y)TaS2does not exfoliate in HzO.
-
-
(A. LERF)
1. R. Schollhorn, A. Weiss, Z . Naturforsch. Teil B, 28, 711 (1973). 2. G. A. Wiegers, R. van der Meer, H. van Heiningen, Muter. Res. Bull., 9, 1261 (1974). 3. G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials. F. Levy, ed., Reidel, Dordrecht, 1979. 4. T. Butz, A. Lerf, J. 0. Besenhard, Rec. Chim. Miner., 21, 556 (1984). 5. R. Schollhorn, A. Weiss, J . Less-Common Met., 36, 229 (1974). 6. R. Schollhorn, R. Arndt, A. Kubny, J . Solid State Chem., 29, 259 (1979). 7. R. Schollhorn, E. Sick, A. Lerf, Muter. Res. Bull., 10, 1005 (1975). 8. F. R. Gamble, J. H. Osiecki, M. Cais, R. Pisharody, F. J. DiSalvo, T. H. Geballe, Science, 174, 493 (1971). 9. W. Biberacher, A. Lerf, F. Buheitl, T. Butz, A. Hubler, Muter. Res. Bull., 17, 633 (1982). 10. R. Schollhorn, in Chemical Physics of Intercalation, A. P. Legrand, S. Flandrois, eds., NATO AS1 Series B, 172, Plenum Press, New York, 1987. 11. W. Biberacher, A. Lerf, J. 0.Besenhard, H. Mohwald,T. Butz, Muter. Res. Bull., 17, 1385 (1982). 12. R. Schollhorn, H. Meyer, Muter. Res. Bull., 9, 1237 (1974). 13. G. V. Subba Rao, J. C. Tsang, Muter. Res. Bull., 9, 921 (1974). 14. C. Riekel, H. G. Reznik, R. Schollhorn, J . Solid State Chem., 34, 253 (1980). 15. T. Butz, A. Lerf, Rev. Chim.Miner., 19, 496 (1982). 16. W. Biberacher, A. Lerf, J. 0. Besenhard, H. Mohwald, T. Butz, S. Saibene, Nuoao Cimento, 2D, 1706 (1983). 17. C. von Wesendonck, W. Biberacher, A. Lerf, Solid State Commun., 74, 183 (1989). 18. R. Schollhorn, Angew. Chern., 92, 1015 (1980). 19. R. Schollhorn, in Intercalation Chemistry, M . S. Whittingham, A. Jacobsen, eds., Academic Press, New York, 1982. 20. C. Ritter, R. Schollhorn, Solid State Comrnun., 61, 117 (1987). 21. A. Lerf, R. Schollhorn, Inorg. Chern., 16, 2950 (1977). 22. D. C. Johnston, J . Less-Common Met., 84, 327 (1982); Muter. Res. Bull., 17, 13 (1982). 23. D. W. Murphy, G. W. Hull, J . Chem. Phys., 62, 967 (1975). 24. C. Liu, 0. Singh, P. Joensen, A. E. Curzon, R. F. Frindt, Thin Solid Films, 113, 165 (1984). 25. P. Joensen, R. F. Frindt, S. R. Morrison, Muter. Res. Bull., 21, 457 (1986). 26. A. S. Golub, G. A. Protzenko, I. M. Yanovskaya, 0. L. Lependina, Y. N. Novikov, Mendel. Cornmun., 199 (1993). 27. M. A. Gee, R. F. Frindt, P. Joensen, S. R. Morrison, Muter. Res. Bull., 21, 543 (1986). 28. M. McKelvy, L. Bernard, W. Glaunsinger, P. Colombet, J . Solid State Chem., 65, 79 (1986). 29. S. P. Hsu. W. S. Glaunsinger, J . Solid State Chern., 67, 109 (1987). 30. P. Colombet, M. Danot, J. Rouxel, W. Glaunsinger, J . Less-Common Met., 156, 413 (1989). 31. M. S. Whittngham, Prog. Sol. State Chern., 12, 41 (1978). 32. A. Lerf, Habilitationsschrift, Munich, 1991. 33. J. 0. Besenhard, H. Meyer, R. Schollhorn, Z . Naturforsch., Teil B, 31, 907 (1976). 34. C. Ramos, Diploma thesis, Munich, 1986. 3.1 1.6.1.6 Molecular Intercalation Compounds
Intercalation of molecules into the layered dichalcogenides is known’. Discovery of superconductivity in some of these’ led to vigorous research activities in this field.
3.11.6 By Insertion Reactions from Solutions 3.11.6.1 Layered Transition Metal Dichalcogenides 3.11.6.1.6 Molecular Intercalation Compounds
283
~~
Molecular intercalation compounds are known from the layered dichalcogenides of the group IVB and VB transition metals [sulfides (mainly 2H-TaS,) > selenides, no tellurides]. Molecules intercalated are-with a few exceptions-aliphatic and aromatic amines or N-containing heterocycles3. The intercalation reactions occur by treatment of the dichalcogenide with excess of the substance to be inserted at temperatures between RT and at most 200°C under exclusion of O2 and H 2 0 . A few new intercalation compounds have been obtained recently: isocyanides4 and some pyrrol and its derivatives were interca1ated5s6.First pyridine intercalation compounds were obtained of the molybdenum-containing mixed dichalcogenides Tal -xMo,S27. For a long time these intercalation compounds were considered to be acid base complexes between the Lewis base molecules and the corresponding Lewis acid solid. However, it has been shown' that nitrogen is deliberated during the intercalation of NH3 in 2H-TaS,; therefore, the intercalation is accompanied by the following reactions 2NH3-N2
+ 6Ht + 6e-
-
H C fNH3-NH; xe-
+ TaS2
[TaS,]
(a) (b)
--x
(4
and the product is a polyelectrolyte compound (see 3.11.6.1.5) that is described as the NH3-solvated compound (NH2)x(NH3)1-x[TaS2] - x : This is confirmed for the ammonia intercalation compounds of TiSZ9and NbS2" also. The product of pyridine ( p y ) intercalation behaves also as the polyelectrolyte compound (pyH+)o.2(py)o.3[TaS2]-o '. The underlying oxidation process should be dimerization of pyridine, or more complex side reactions". The expected dimerization products were not found in experiments under rigorously controlled conditions'2. Therefore, it has been assumed that pyridinium formation is caused by traces of H 2 0 and the reduction of TaS, by sulfide ions liberated from the solid by the hydrolysis (see 3.11.6.1.5)13.The effect of H 2 0 on the intercalation of molecules is very complicated 1 2 , and there are other unexplained results in the py/TaS2 system: e.g., the intercalation of pure pyridine leads to two slightly different layer distances (11.8 and 12 A), whereas only one layer distance (12 A) has been observed if sulfur is added to the reaction mixture14. The two compounds differ in thermal decomp~sition'~. The first decomposes in two steps starting at about 80 and 300°C; the decomposition of the second starts at 300°C. The very high decomposition temperature is indicative of an oligomeric organic species whose nature is still unclear. It has been proposed' for the hydrazine intercalation compounds of lamellar dichalcogenides, that oxidation of the strongly reducing hydrazine occurs without the expected release of gaseous nitrogen. This mechanism assumes formation of tetrazane and protons so that no evidence for neutral hydrazine can be found from the optical data. Considering the oxidation chemistry of amines, it is to be expected that intercalation of most amines may be accompanied by oxidation of the nitrogen-containing molecul e ~ The ~ ~key . step could be the formation of an aminium radical, which may loose protons from the z carbon, where upon either dimerization or oxidation and nucleophilic attack occurs. This assumption has to be verified, and thus each amine intercalation compound has to be studied separately. Physical methods support the oxidation model. The diamagnetic susceptibility of the NH3 intercalation compound is of the same order as for the Li intercalation compound of the same charge transferg. Charge transfer data obtained for about 10 different
284
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 La ered Transition Metal Dichalcogenides 3.11.6.1.7 Zomplex Intercalated Species ~
~~
intercalation compounds indicate that the oxidation model could be valid for more compounds than those studied in detai1.'5%'6 If the above model is of general importance, the molecular intercalation compounds would be nothing else than solvated phases of H,TaS216. The observation that only N-containing molecules with a pK, value higher than 4 form intercalation compounds1' would get a new interpretation; it would appear that only the compounds forming stable protonated salts with weak acids can be intercalated and form stable intercalation compounds. New molecular intercalation compounds, even of MoS2, have been obtained by exfoliation and flocculation (see 3.11.6.1.7). (A. LERF)
1. A. Weiss, R. Ruthardt, Z . Naturforsch., Teil B, 24, 256, 355, 1066 (1969). 2. F. R. Gamble, J. H. Osiecki, M. Cais, R. Pisharody, F. J. DiSalvo, T. H. Geballe, Science, 174, 493 (1971). 3. G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials, F. Levy, ed., Reidel, Dordrecht, 1979. 4. M. B. Dines, Inorg. Chem., 17, 762 (1978). 5. H. U. Hummel, R. Fackler, H. Adrian, M. Lippert, Z . Anorg. Allg. Chem., 575, 165 (1989). 6. H. U. Hummel, R. Fackler, P. Remmert, Z . Naturforsch., Teil B, 47, 741 (1992). 7. P. Remmert, H. U. Hummel, Z . Naturforsch., Teil B, 49, 1387 (1994). 8. R. Schollhorn, H. D. Zagefka, Angew. Chem., Int. Ed. Engl., 16, 199 (1977). 9. L. Bernard, M. McKelvy, W. Glaunsinger, P. Colombet, Solid State lonics, 15, 301 (1985). 10. J. M. Dunn, W. Glaunsinger, Solid State lonics, 27, 285 (1988). 11. R. Schollhorn, H. D. Zagefka, T. Butz, A. Lerf, Mater. Res. Bull., 14, 369 (1979). 12. J. F. Lomax, B. N. Diel, T. J. Marks, Mol. Cryst. Liquid Cryst., 121, 145 (1985). 13. P. Colombet, V. Cajipe, Eur. J. Solid State Inorg. Chem., 26, 255 (1989). 14. A. J. Thompson, Nature, 251, 492 (1974). 15. D. C. Johnston, Sol. State Comm., 43, 533 (1982). 16. R. Schollhorn, in Inclusion Compounds, Vol. 1, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, eds., Academic Press, London, 1984. 17. F. R. Gamble, J. H. Osiecki, F. J. DiSalvo, J . Chem. Phys., 55, 3525 (1971). 3.1 1.6.1.7 Complex Intercalated Species
Section 3.11.6.1.6 described intercalation compounds of N-containing molecules (mainly organics). Here we treat all such intercalates that are mainly neutral organometallic compounds acting as their own reducing agent, or cations (organometallic not stable in the neutral form, organic, inorganic cluster cations) and polymers. (i) Neutral Organometallic Compounds. Neutral reducing metallocene complexes are intercalated by treating powdered dichalcogenides with solutions of the complex in toluene at about 130"C1-3.Intercalation occurs for the dichalcogenides MX2 (M = Ti; The intercalate content Zr, Hf, V; Nb, Ta, Sn, mostly sulfides, only a few ~elenides)~. varies (0.08 < x < 0.42) depending on the type of host lattice and the metallocene. Magnetic susceptibility measurements indicate a complete charge transfer to the conduction band. From NMR measurements it can be deduced that the c5 axis is oriented parallel to the host layer^^-^. A series of derivatives substituted in the organic part could also be inserted in the interlayer gap3. Recently it has been shown that [CoCp:],SnS2 can be lithiated by BuLi treatment; [CoCp:] is converted to the neutral form in this reaction6. It should be mentioned that the intercalation compound [ C O C ~ ~ ] , . ~is Sa superconductor ~S~~ with a T c of 8.1 K, the highest Tc value of an intercalation compound of the layered dichalcogenides'.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
284
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.1 La ered Transition Metal Dichalcogenides 3.11.6.1.7 Zomplex Intercalated Species ~
~~
intercalation compounds indicate that the oxidation model could be valid for more compounds than those studied in detai1.'5%'6 If the above model is of general importance, the molecular intercalation compounds would be nothing else than solvated phases of H,TaS216. The observation that only N-containing molecules with a pK, value higher than 4 form intercalation compounds1' would get a new interpretation; it would appear that only the compounds forming stable protonated salts with weak acids can be intercalated and form stable intercalation compounds. New molecular intercalation compounds, even of MoS2, have been obtained by exfoliation and flocculation (see 3.11.6.1.7). (A. LERF)
1. A. Weiss, R. Ruthardt, Z . Naturforsch., Teil B, 24, 256, 355, 1066 (1969). 2. F. R. Gamble, J. H. Osiecki, M. Cais, R. Pisharody, F. J. DiSalvo, T. H. Geballe, Science, 174, 493 (1971). 3. G. V. Subba Rao, M. W. Shafer, in Intercalated Layered Materials, F. Levy, ed., Reidel, Dordrecht, 1979. 4. M. B. Dines, Inorg. Chem., 17, 762 (1978). 5. H. U. Hummel, R. Fackler, H. Adrian, M. Lippert, Z . Anorg. Allg. Chem., 575, 165 (1989). 6. H. U. Hummel, R. Fackler, P. Remmert, Z . Naturforsch., Teil B, 47, 741 (1992). 7. P. Remmert, H. U. Hummel, Z . Naturforsch., Teil B, 49, 1387 (1994). 8. R. Schollhorn, H. D. Zagefka, Angew. Chem., Int. Ed. Engl., 16, 199 (1977). 9. L. Bernard, M. McKelvy, W. Glaunsinger, P. Colombet, Solid State lonics, 15, 301 (1985). 10. J. M. Dunn, W. Glaunsinger, Solid State lonics, 27, 285 (1988). 11. R. Schollhorn, H. D. Zagefka, T. Butz, A. Lerf, Mater. Res. Bull., 14, 369 (1979). 12. J. F. Lomax, B. N. Diel, T. J. Marks, Mol. Cryst. Liquid Cryst., 121, 145 (1985). 13. P. Colombet, V. Cajipe, Eur. J. Solid State Inorg. Chem., 26, 255 (1989). 14. A. J. Thompson, Nature, 251, 492 (1974). 15. D. C. Johnston, Sol. State Comm., 43, 533 (1982). 16. R. Schollhorn, in Inclusion Compounds, Vol. 1, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, eds., Academic Press, London, 1984. 17. F. R. Gamble, J. H. Osiecki, F. J. DiSalvo, J . Chem. Phys., 55, 3525 (1971). 3.1 1.6.1.7 Complex Intercalated Species
Section 3.11.6.1.6 described intercalation compounds of N-containing molecules (mainly organics). Here we treat all such intercalates that are mainly neutral organometallic compounds acting as their own reducing agent, or cations (organometallic not stable in the neutral form, organic, inorganic cluster cations) and polymers. (i) Neutral Organometallic Compounds. Neutral reducing metallocene complexes are intercalated by treating powdered dichalcogenides with solutions of the complex in toluene at about 130"C1-3.Intercalation occurs for the dichalcogenides MX2 (M = Ti; The intercalate content Zr, Hf, V; Nb, Ta, Sn, mostly sulfides, only a few ~elenides)~. varies (0.08 < x < 0.42) depending on the type of host lattice and the metallocene. Magnetic susceptibility measurements indicate a complete charge transfer to the conduction band. From NMR measurements it can be deduced that the c5 axis is oriented parallel to the host layer^^-^. A series of derivatives substituted in the organic part could also be inserted in the interlayer gap3. Recently it has been shown that [CoCp:],SnS2 can be lithiated by BuLi treatment; [CoCp:] is converted to the neutral form in this reaction6. It should be mentioned that the intercalation compound [ C O C ~ ~ ] , . ~is Sa superconductor ~S~~ with a T c of 8.1 K, the highest Tc value of an intercalation compound of the layered dichalcogenides'.
3.11.6 By Insertion Reactions from Solutions 3.1 1.6.1 La ered Transition Metal Dichalcogenides 3.1 1.6.1.7 8omplex Intercalated Species
285
(ii) Intercalation of Cations. There are three methods for intercalation of cations: ion exchange, electrointercalation out of aqueous or nonaqueous solutions of salts containing the cation to be intercalated, and the flocculation method. The first method has been used to intercalate the organometallic complex cations [Fe(2,2'dipyridine),]" ', [(q-CSH5)(y-C6H6)Fe] or [(q-C,H,),Cr] ', the polyoxycation [A104Al12(0H)24(H20)12]7+(A113)', and also alkylammonium '. The electrochemical intercalation of complex cations in pristine 2H-TaSz has been d e m o n ~ t r a t e d ' ~ The ~ ' ~ . species intercalated range from aromatic and aliphatic ammonium to carbonium13 and trimethylsulfonium cation^'^, organometallic complex cations [Fe(2,2'-dipyridir1e)~]'+,[Fe(phenanthrolir~e),]~+, [y-C6H&Cr] +,[(qC5H6)5Co]+ I 3 , metal complexes with inorganic ligandsL3, cryptate complexes (Ba(K222)" I 3 and La(K222)3+I 4 and dye molecule cations13. In case of [(yCSH6),Co]+,reaction starts at low formal intercalate content with a two-phase region (2H-TaS2/first-stage phase). The reaction is finished at 0.25 e-/TaSz as indicated by a potential stepI3. This agrees well with the cobaltocene content in the thermally prepared sample3. Intercalation of the La(K222)-complex starts also in a two-phase system (2H-TaSz/first-stage phase) and is finished at a charge transfer II = 0.18 e-/TaSz, which corresponds to an intercalate content of 0.06 due to La3+. Recently the successful intercalation of dye molecule cations (methylene blue and paraquat) in crystals of 2H-TaS, was shown, but reaction is superposed by side reactions and only the dilatometer record allowed determination of the end of the reaction. In case of methylene blue three different phases could be obtained (molecule monolayers parallel to the host layers, bilayers, staggered arrangement nearly perpendicular to the host layers)' 5 . +
+
(iii) Intercalationby Exfoliation/Flocculation Procedures. New intercalation compounds have been prepared by this method, e.g., for MoS, and 2H-TaS,. The reaction follows the sequence MSZ-
A,MS,-
dispersion
+ A'-
A,-,.A',,MS,
(a)
To obtain TaSZ- colloids 2H-TaS2 will be reduced in 50/50 mixtures of N M F and H 2 0 with sodium dithionite to give the intermediate phase Nao.33(H20),TaSz16.This solid swells immediately if it is placed after washing with distilled H z O in N M F and H 2 0 added. For the preparation of the MoSz colloid, Li,MoSz is first prepared by the BuLi method, and this compound is exposed to H 2 0 ,where a vigorous reaction occurs. Rapid reaction accompanied by the evolution of H z gas causes the layers to be blown apart and opaque suspension to form: Ultrasonication can assist exfoliation, and the addition of a surfactant enhances the stability. In the latter case it is not clear whether residual charges remain on the solid; the formation of A,(H20),MoS2 would support this viewI6. Aggregation of the colloids is induced by increasing the ionic strength of the solution or by decreasing the dielectric constant. Cations of the electrolyte or the solvents applied to induce the flocculation can be occluded in the precipitated solidI6. This method has been used to form intercalation compounds of large cluster cations, unusual solvents, and polymers not accessible by the conventional methods of intercalation. Cations included into layer host lattices are, e.g., [(y-C,H,),Co] 1 7 , the chalcogenide clusters (Fe6s8(PEt3)3]2+1 7 , 1 8 , the A113, the gallium polyoxycations" and cyanine dyesIg in 2H-TaSz, and the chalcogenide cluster [ C O ~ Q ~ ( P R(with ~ ) ~Q] = S, Se, Te)20in MoSz. The latter example and the solvent inclusion complexes (e.g., 1-hexene, benzene, +
286
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.2 Other Layered Chalcogenides 3.1 1.6.2.1 Ta,S2C, N$S,C
heptane”, or tetrachloroethylene22) support the assumption of uncharged MoSz layers in the colloid. By this method thtee different polymers have been included in MoS2: polystyrene (layer distance 12.3 A)21, p~lyaniline’~,and polyethyleneoxide-solvated lithi~m~~,~
’.
(A. LERF)
1. M. B. Dines, Science, 188, 1210 (1975). 2. R. P. Clement, W. B. Davies, K. A. Ford, M. L. H. Green, A. J. Jacobson, Inorg. Chem., 17,2754 (19781. 3. A. J. Jacobson in, Intercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. 4. F. R. Gamble, A. H. Thompson, Solid State Commun., 27, 379 (1978). 5. B. G. Silbernagel, Chem. Phys. Lett., 34, 298 (1975). 6. D. G. Clerc, D. A. Cleary, Chem. Mater., 6, 13 (1994). 7. D. O’Hare, C. Formstone, J. Hodby, M. Kermoo, E. FitzGerald, P. A. Cox, J . Chem. Soc., Chem. Commun., 11 (1990). 8. A. Lerf, Ph.D. thesis, Munich, 1976. 9. A. Lerf, E. Lalik, W. Kolodziejski, J. Klinowski, J . Phys. Chem., 96, 7389 (1992). 10. R. Schollhorn, A. Weiss, J . Less-Common Met., 36, 229 (1974). 11. R. Schollhorn, in Zntercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. 12. G. V. Subba Rao, J. C. Tsang, Mater. Res. Bull., 9, 921 (1974). 13. C. Riekel, H. G. Reznik, R. Schollhorn, J . Solid State Chem., 34, 253 (1980). 14. C. Ramos, Diploma thesis, Munich (1986); A. Lerf, Habilitationsschrift, Munich, 1991. 15. A. Hauptmann, A. Lerf, W. Biberacher, Z. Naturforsch., Teil B, 51, 1571 (1996). 16. A. J. Jacobson, in Comprehensive Supramolecular Chemistry, Vol. 7, G. Alberti, T. Bein, eds., Pergamon Press, Oxford, 1996. 17. L. F. Nazar, A. J. Jacobson, J . Chem. Soc., Chem. Commun., 570 (1986). 18. L. F. Nazar, A. J. Jacobson, J . Mater. Chem., 4, 1419 (1994). 19. D. W. Murphy, G. W. Hull, J . Chem. Phys., 62, 967 (1975). 20. R. Bissessur, J. Heising, W. Hirpo, M. Kanatzidis M., Chem. Mater., 8, 318 (1996). 21. W. M. R. Divigalpitiya, R. F. Frindt, S. R. Morrison, Science, 246, 369 (1989). 22. X. Zhou, D. Yang, R. F. Frindt, J . Phys. Chem. Solids, 57, 1137 (1996). 23. M. G. Kanatzidis, R. Bissessur, D. C. Degroot, J. L. Schindler, C. R. Kannewurf, Chem. Mater., 5 , 595 (1993). 24. E. Ruiz-Hitzky, R. Jimenez, B. Casal, V. Manriquez, A. Santa Ana, G. Gonzalez, Adv. Mater., 5, 738 (1993). 25. J. P. Lemmon, M. M. Lerner, Chem. Mater., 6, 207 (1994). \
I
3.11.6.2 Other Layered Chalcogenides 3.1 1.6.2.1 Ta,S,C, Nb&C
The MzSZCslabs are built up by S, Ta, C layers in the sequence S-Ta-C-Ta-S. Within these slabs there are strong covalent bonds. The intercalation chemistry of Ta&C resembles that of 2H-TaS2.The following species could be inserted: (1) transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, xmax= 0.25-0.33; Cu, x = 0.7) by thermal reactions at 1000°C’; (2) alkali metals (Li, Na, K, Rb, Cs) from their NH3 solutions’ (the compounds have restricted homogeneity ranges depending on the alkali metal; Li occupies octahedral lattice sites in the interlayer gap; K, Rb, and Cs are in trigonalprismatic sites; and Na as the borderline case exhibits both coordinations); (3) the hydrated sodium compound by chemical reduction with sodium dithionite3; (4) other hydrated alkali and alkaline earth metal and alkylammonium cations by ion exchange3; and (5) organic molecules (as in the case of the layered dichalcogenides) at temperatures between 20 and 170°C under exclusion of oxygen4.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
286
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.2 Other Layered Chalcogenides 3.1 1.6.2.1 Ta,S2C, N$S,C
heptane”, or tetrachloroethylene22) support the assumption of uncharged MoSz layers in the colloid. By this method thtee different polymers have been included in MoS2: polystyrene (layer distance 12.3 A)21, p~lyaniline’~,and polyethyleneoxide-solvated lithi~m~~,~
’.
(A. LERF)
1. M. B. Dines, Science, 188, 1210 (1975). 2. R. P. Clement, W. B. Davies, K. A. Ford, M. L. H. Green, A. J. Jacobson, Inorg. Chem., 17,2754 (19781. 3. A. J. Jacobson in, Intercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. 4. F. R. Gamble, A. H. Thompson, Solid State Commun., 27, 379 (1978). 5. B. G. Silbernagel, Chem. Phys. Lett., 34, 298 (1975). 6. D. G. Clerc, D. A. Cleary, Chem. Mater., 6, 13 (1994). 7. D. O’Hare, C. Formstone, J. Hodby, M. Kermoo, E. FitzGerald, P. A. Cox, J . Chem. Soc., Chem. Commun., 11 (1990). 8. A. Lerf, Ph.D. thesis, Munich, 1976. 9. A. Lerf, E. Lalik, W. Kolodziejski, J. Klinowski, J . Phys. Chem., 96, 7389 (1992). 10. R. Schollhorn, A. Weiss, J . Less-Common Met., 36, 229 (1974). 11. R. Schollhorn, in Zntercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. 12. G. V. Subba Rao, J. C. Tsang, Mater. Res. Bull., 9, 921 (1974). 13. C. Riekel, H. G. Reznik, R. Schollhorn, J . Solid State Chem., 34, 253 (1980). 14. C. Ramos, Diploma thesis, Munich (1986); A. Lerf, Habilitationsschrift, Munich, 1991. 15. A. Hauptmann, A. Lerf, W. Biberacher, Z. Naturforsch., Teil B, 51, 1571 (1996). 16. A. J. Jacobson, in Comprehensive Supramolecular Chemistry, Vol. 7, G. Alberti, T. Bein, eds., Pergamon Press, Oxford, 1996. 17. L. F. Nazar, A. J. Jacobson, J . Chem. Soc., Chem. Commun., 570 (1986). 18. L. F. Nazar, A. J. Jacobson, J . Mater. Chem., 4, 1419 (1994). 19. D. W. Murphy, G. W. Hull, J . Chem. Phys., 62, 967 (1975). 20. R. Bissessur, J. Heising, W. Hirpo, M. Kanatzidis M., Chem. Mater., 8, 318 (1996). 21. W. M. R. Divigalpitiya, R. F. Frindt, S. R. Morrison, Science, 246, 369 (1989). 22. X. Zhou, D. Yang, R. F. Frindt, J . Phys. Chem. Solids, 57, 1137 (1996). 23. M. G. Kanatzidis, R. Bissessur, D. C. Degroot, J. L. Schindler, C. R. Kannewurf, Chem. Mater., 5 , 595 (1993). 24. E. Ruiz-Hitzky, R. Jimenez, B. Casal, V. Manriquez, A. Santa Ana, G. Gonzalez, Adv. Mater., 5, 738 (1993). 25. J. P. Lemmon, M. M. Lerner, Chem. Mater., 6, 207 (1994). \
I
3.11.6.2 Other Layered Chalcogenides 3.1 1.6.2.1 Ta,S,C, Nb&C
The MzSZCslabs are built up by S, Ta, C layers in the sequence S-Ta-C-Ta-S. Within these slabs there are strong covalent bonds. The intercalation chemistry of Ta&C resembles that of 2H-TaS2.The following species could be inserted: (1) transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, xmax= 0.25-0.33; Cu, x = 0.7) by thermal reactions at 1000°C’; (2) alkali metals (Li, Na, K, Rb, Cs) from their NH3 solutions’ (the compounds have restricted homogeneity ranges depending on the alkali metal; Li occupies octahedral lattice sites in the interlayer gap; K, Rb, and Cs are in trigonalprismatic sites; and Na as the borderline case exhibits both coordinations); (3) the hydrated sodium compound by chemical reduction with sodium dithionite3; (4) other hydrated alkali and alkaline earth metal and alkylammonium cations by ion exchange3; and (5) organic molecules (as in the case of the layered dichalcogenides) at temperatures between 20 and 170°C under exclusion of oxygen4.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.2 Other Layered Chalcogenides 3.1 1.6.2.3 MPX,
287
The alkali metal content of the hydrated phases is x = 0.2, less than in the corresponding 2H-TaS2 compounds. These phases are more sensitive to deintercalation by oxygen than those of 2H-TaSz3.A higher tendency toward decomposition is observed for the Cu compound, which decomposes to Cu and Ta2SzC. Thermal treatment can reverse this reaction'. The isostructural compound Nb2S2C cannot be prepared directly; the only stable ternary carbide in the Nb-S-C system is Nb2SC1 - X . Treating this compound with sulfur and the transition metals at around 1000°C gives the quaternary compounds (M,Nb&C) [x is about twice as high as in M,(Ta2S2C)], which are isostructural to the corresponding Ta2S2C compounds. Treatment of Cuo.,(NbzSzC) with HCl yields the ternary compound Nb2S2C as a metastable phase5. 3.1 1.6.2.2 K2Pt4SSand A2M3S4
In KzPt4S6 the Pt& units form an S-Pt-S arrangement, but one-quarter of the possible sulfur positions remain unoccupied. The Pt atoms occur in two oxidation states; the quadrivalent Pt have octahedral coordination, whereas the rest correspond to Pt(I1) with planar coordination by sulfur. The compound K2Pt4S6 in contact with oxygen-saturated water undergoes spontaneous hydration to K,(H20)y[Pt4S6]X-.In the course of this reaction potassium ions are released to a residual x 1 (cf. hydration of NaCrSz, 3.11.6.1.5). This compound exhibits rapid ion exchange with alkaline earth ions, transition metal ions, and organic cations. The observed layer distances and hydration and solvation behavior show some analogy to the corresponding phases of the layered dichalc~genides~,~. Anodic oxidation in aqueous mineral acids yields Pt4S6,which is a metastable compound and decomposes at 200°C'. The layered sulfides Cs2Pd3S4,K2Pd3S4,and Cs2Pt3S4 are similar in structure to K2Pt4S6,but the transition metal atoms are positioned exclusively in planar sulfur coordination. Whereas hydration and cation exchange proceed slowly with metal cations, quantitative ion exchange can be achieved with alkylammonium ions'. The structure of K2Ni3S4 is not known, but the crystal morphology suggests a layer-type structure, which was confirmed by the hydration and ion exchange behavior. Like K2Pt4S6, this compound forms in contact with air-saturated water as the hydrated phase K,(H20),[Ni3S4]"- with x 1.5. This compound is accessible to ion exchange and solvation reactions. Anodic oxidation can lower the potassium content further to x = 0.9; this phase also undergoes solvation and ion exchange reactions'.
-
-
3.1 1.6.2.3 MPX3
The structure of this compound series can be described by analogy to the CdC12type structure. The sulfur atoms are in an essentially close-packed cubic array; every second layer of octahedral sites is empty, whereas the remaining layers of octahedral sites are completely occupied by metal atoms and phosphorus atom pairs (P2).This structure has been adopted by compounds with M = Mg, V, Mn, Fe, Co, Ni, Zn, Pd, Cd, and X = S. Selenium forms similar structures with M = Mg, Mn, Fe, Ni, and Cd. Other variations include compounds with metal vacancies and phases with two different metal atoms*-' The MPX3 compounds show two distinct kinds of intercalation chemistry". Redox intercalation reactions analogous to those of the layered dichalcogenides are observed for
288
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.2 Other Layered Chalcogenides 3.1 1.6.2.4 Li,FeS,, LiCuFeS,, NaCuFeS, and KCuFeS,
FePS3, Nips3, and FePSe,. The second reaction type involves an ion exchange process whereby loss of M cations from the MPX3 layers into the solution phase maintains charge balance on intercalation of cations between the layers. The redox intercalation chemistry is focused mainly on Li intercalation because it is of interest in the application of the compounds as cathodes in secondary batteries. Lithium intercalation is carried out by the BuLi method and electrochemically. Reaction of NiPS3 with excess BuLi leads to a composition Li,NiPS3 with x > 3, which is much greater than the maximum x value expected from the number of possible lattice sites (lithium sulfide formation). Controlled intercalation shows two distinct homogeneity regions with 0 < x < 0.5 and 0.5 < x < 1.5. No lattice expansion is observed, but intercalation can be demonstrated by formation of the hydrated phase on exposure to H20. Both FePS3 and NiPS3 react with toluene solutions of cobaltocene to give intercalation compounds that are similar in composition and layer distance to the corresponding phases formed by the transition metal dichalcogenides. Similar compounds were formed by reaction of MnPS3, ZnPS3, and CdPS3 with solutions of metallocene salts, but this reaction proceeds by the second reaction type mentioned above: by ion exchange with M 2 + cations from the layers to form compounds with the stoichiometry (MCp&[Mnl -,O,PS31. YHzO. Compounds Al,[Mnl-,O,PS3] .yH20 with A = alkali metal and alkylammonium ions have been prepared by this second method too. The extent of cation exchange is restricted to x 0.15 (the only exception is Na' with x = 0.5)10s12.
-
3.11.6.2.4 Li,FeS,, LiCuFeS,, NaCuFeS, and KCuFeS,
The high mobility of lithium ions in LizFeSz renders this compound accessible to oxidative deintercalation and reductive reintercalation. Oxidation can be carried out chemically by iodine/MeCN, or electrochemically in a LiC104/dioxolane electrolyte. During successive deintercalations, three different phases appear in the stoichiometry range 0 < x < 2: Li,FeSz(v) with 1.5 < x < 2, LizFe&(y) corresponding to 1.09 < x < 1.5, and a highly oxidized phase LizFeSZ(1,)with x < 0.0213.Between the v- and ?-phases there is a potential drop. From Li .1FeS2 to FeS2 a potential plateau reveals a two-phase domain. Chemical reintercalation through the BuLi method allows one to reach Lil.sFeSz, but it is difficult to go further. These deintercalation and reintercalation reactions are accompanied by severe restructuring within the host lattice, as well as complex oxidation proce~ses'~. The structure of Li,FeSz is based on a hexagonal-close-packed arrangement of sulfur atoms (slightly distorted from ideal close-packing by greater expansion in the a, b directions). Half the lithium ions occupy octahedral sites between the "S-Fe-S" layers; the other half are located together with the iron atoms on the tetrahedral holes within the layer^'^. Deintercalation of Li results in oxidation of Fe(I1) to Fe(II1); around Li1.5FeS2 iron atoms begin switching to octahedral coordination. This transition is related to a drastic potential change and the difficulty of increasing x above 1.5 during intercalation. From Li - 1FeS2 to FeS2, further oxidation affects sulfur with the occurence of (Sz)2- pairs; thus the electronic structure of FeS2 is described by the following formula; Feb'f5co,Fe'd.5c~,S2-(S~)~ < . The charge balance of this compound is between that of the (two-dimensional) Ti'"& and (three-dimensional) Fe"S2 12. LiCuFeSz and NaCuFeS2 crystallize with the LiZFeSz-type structure; Cu and Fe occupy randomly the tetrahedral sites, and the lithium or sodium atoms are located on octahedral sites in the CuFeS2 interlayer gallerie~'~.''.In the Li compound the copper
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.2 Other Layered Chalcogenides 3.11.6.2.5 KCu,S,
289
atoms of the CuFeSz layers move to the van der Waals gap if Li is removed by oxidation". Unlike the related Na and Li phases, KCuFeSz crystallizes in the ThCrzSiz-type structure, where the tetrahedra around the transition metals are regular. The potassium ions occupy cubic sites between the CuFeSz layers, in contrast to the layer dichalcogenides where K is octahedrally or trigonal-prismatically coordinated". Treating this phase with HzO leads to removal of potassium ions, and the resulting compound takes up poly ethylene oxide from an aqueous solution of the polymer". Longer periods of HzO treatment lead to an irreversible loss of crystallinity". It is possible that the H20-treated crystalline phase contains some potassium, which can be solvated by the polymer. 3.11.6.2.5 KCu,S,
The structure of KCu4S3 consists of [CU&]- layers held together by potassium ions. The layers consist of CuS4 tetrahedra sharing edges and vertices. Electrochemical reduction in a CuCl/acetonitrile electrolyte leads to an uptake of Cu' into the [Cu4S3]layers on octahedral sites and the simultaneous change of the oxidation state of some sulfur atoms as: K [(Cu:)4(S2 +
-)2
(S' -)1]
+ Cu' + e --K
+
[(Cu:)4(Cuo')l(SZ -131
(a)
The composition of the new compound is KCu5S3, and X-ray diffraction analysis shows that the tetragonal symmetry is retained. Hence the whole reaction is a topotactic transformation of the host (A. LERF)
1. 2. 3. 4. 5. 6. 7.
8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21.
H. Boller, R. Sobczak, Monatsh. Chem., 102, 1226 (1971). R. Brec, J. Ritsma, G. Ouvrard, J. Rouxel, Inorg. Chem., 16, 660 (1977). R. Schollhorn, W. Schmucker, Z . Naturforsch., Teil B, 30, 975 (1975). R. Schollhorn, A. Weiss, Z . Naturforsch., Teil B, 28, 716 (1973). H. Boller, K. Hiebl, J . Alloys Comp., 183, 438 (1992). R. Schollhorn, in Reactiz;ity ofSolids, J. Wood, 0. Lindqvist, C. Helgesson, N. G. Vannerberg, eds., Plenum Press, New York, 1977. R. Schollhorn, in Intercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. J. W. Johnson, in Intercalation Chemistry, M. S. Whittingham, A. J. Jacobson, eds., Academic Press, New York, 1982. R. Brec, Solid State Ionics, 22, 3 (1986). A. J. Jacobson, in Solid State Chemistry-Compounds, A. K. Cheetham, P. Day, eds., Clarendon Press, Oxford, 1992. J. Rouxel, in Inorganic Reactions and Methods, Vol. 17, G. P. Hagen, ed., VCH, New York, 1990. R. Clement, J. P. Audiere, J. P. Renard, Rez;. Chim. Miner., 19, 560 (1982). R. Brec, A. Dugast, A. Le Mehaute, Mater. Res. Bull., 1.5, 619 (1980). L. Blandeau, G. Ouvrard, Y. Calage, R. Brec, J. Rouxel., J . Phys. C, Solid State Phys., 20, 4271 (1987). R. L. Batchelor, F. W. B. Einstein, C. H. W. Jones, R. Fong, J. R. Dahn, Phys. Reu. B, 37, 3699 11988). R. M.'Fong, J. R. Dahn, R. L. Batchelor, F. W. B. Einstein, C. H. W. Jones, Phys. Rez;.B, 39,4424 (1989). J. Llanos, C. Contreras-Ortega, C. Mujica, H. G. von Schnering, K. Peters, Mater. Res. Bull., 28, 39 (1993). C. Mujica, J. Paez, J. Llanos, Mater. Res. Bull., 29, 263 (1994). C. Mujica, R. Duran, J. Llanos, R. Clavijo, Mater. Res. Bull., 31, 483 (1996). F. Viola, R. Schollhorn, J . Chem. Soc., Chem. Commun., 907 (1992). M. Schmalz, F. Viola, R. Schollhorn, R. Schlogl, Mater. Res. Bull., 28, 1311 (1993).
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc. 290
3.11.6 By Insertion Reactions from Solutions 3.11.6.3 Chain Stuctures 3.1 1.6.3.2 KFeS,
3.1 1.6.3 Chain Stuctures 3.1 1.6.3.1 The Pseudo-One-Dimensional Compounds MX:,
The transition metal trichalcogenides MX3 [a better description might be M4+(X2)'-X2-; M = Ti, Zr, Hf, Nb, Ta; X = S, Se] consist of MX3 slabs held together by van der Waals forces [the (S2)'- are directed towards the van der Waals gap]. Each MX3 slab is built up of trigonalprismatic MX3 chains such that two rectangular faces of an MXs prism are capped by X atoms of neighboring MX3 chains. The type of connection between the MX3 chains leads to different structural variants'. Lithium intercalation in the crystalline MX3 compounds has been performed through the BuLi technique' or electrochemically3. Using the BuLi method, three Li atoms per MX3 can be incorporated into the host structure without disruption'. The extension of two-phase and single-phase regions with increasing Li content depends on MX3 and the method of inter~alation'-~. Within the homogeneity ranges the intercalation/deintercalation is a reversible p r o ~ e s s l - ~ . From the complete disappearance of the polysulfide peak in the IR spectra it has been concluded that the first two electrons are used to break the (X2)'- bonds4.The third electron is believed to reduce the metal. Recent considerations of band structure show that the (X2)'- bond breaking is a three-electron process, in agreement with the observation of chemical intercalation6.Spectroscopic investigations show that the electronic state of the transition metal is not changed significantly during intercalation but makes it probable that the electrons could be localized near the Li atoms (strong interactions between Li and S, Li in tetrahedral c~ordination)~~'. The Li ions are highly disordered not only in the interlayer gap but also between the chains4.'. Extended X-ray Absorption Fine Structure (EXAFS) studies on Li,NbS3 show the reduction of the coordination number of Nb, which is indicative of breaking of the bicapping bonds'. 3.1 1.6.3.2 KFeS,
The compound KFeS2 has a structure built up from infinite chains of edge-shared [FeS,] - tetrahedra. The K ions occupy interchain sites and are eightfold coordinated in distorted squares antiprismatic sites. The interchain potassium ions are readily exchangeable in aqueous solution^^^'^. Exchange by Cu' and Ag' is accompanied by migration of Fe3+ ions from chain to interchain sites; the final products MFeSz (with M = Cu, Ag) have the chalcopyrite structure". Other exchange reactions occur with preservation of the chain structure. Reactions with aqueous solutions of alkaline earth metal chlorides lead to formation of hydrated phases (A2+)o.sFeS2.yHz0(M = Ca, Sr) and to the anhydrous Bao,5FeSz'o. The Sr Prolonged compound is dehydrated easily without destruction of the compound' exchange in aqueous NaCl solution leads to complete replacement of the K + and the formation of NaFeSz. 2H20. By ion exchange in aqueous lithium salt solutions, the solid gradually disperses and a green colloid solution is formed'. Similar solutions can be prepared by addition of excess NaSH or KSH to ferric nitrate solutions in the pH range 11-12. Addition of acetone or 1 M solutions of MOH causes irreversible precipitation of NaFeSz .2H20 and K F ~ S Z ' . ' ~The . mixed-valent compound NasFe'S4, which contains twisted [FeSzI-chains, is oxidized in air and hydrated to NaFeS'. 2H2OI4. It is possible to insert Li in KFeS2 with the BuLi method or electrochemically (nonaqueous conditions!). This additional Li uptake is a two-phase reaction where '9".
3.1 1.6 By Insertion Reactions from Solutions 3.11.6.3 Chain Stuctures and [Mo3X3]= 3.1 1.6.3.3 A,[Mo,X,]
291
monoclinic KFeS2 is converted to the body-centered tetragonal KLi,FeSz(x = l ) I 5 , l 6 ; from this compound Li can be removed by oxidation easily to x = 0.6 or very slowly to x = 0.3-0.4 without changing the structure. Within the region 0.4 < x < 1, a reversible electron transfer/Li uptake is p o s ~ i b l e ' ~ . ' ~ . 3.1 1.6.3.3 A,[Mo,X,] and [Mo,XJ These compounds contain infinite chains of staggered Mo triangles surrounded by chalcogenide atoms bridging Mo atoms. The chains are formed by fusion of [ M o ~ X ~ ] units along their C3 axis by a loss of two capped chalcogen atoms (those lying on the C3 axis) and sharing faces. The chalcogen atoms bridge four Mo atoms of edge-shared triangular phases of the condensed Mo octahedra. These chains are separated by the charge compensating ternary element (metal cations). The following compounds are known: for X = S those with A = K, Rb, Cs; for X = Se with A = Li, Na, K, Rb, Cs, Ba, In, T1; and for X = Te those with Na, K. Rb, Cs, Ba, In, Tl". The metastable alkali metal compounds can be prepared from Inz[MO6Se6] and In~[Mo6Te6] by ion exchange in molten halidesI8. The indium halides formed in this process are volatile and can be separated easily from the solid in a temperature gradient. Apart from the alkali metal compounds mentioned, it is also possible to exchange In by Ag, Cu, Pb, and Sn in case of the ~ e l e n i d e s ' ~ . 'Mixing ~. appropriate amounts of Inz[Mo6X6] and metal salts and heating yields compounds Inz-xAx[M06X6] with x ranging from 0 to 218. In In2-,LiX[Mo,$e6] the lithium ion can be removed to form In2-,A,[Mo6Se6] (0 < x < 1.8) by treatment with iodine in MeCN at RT18. The new binaries [MO~X,]are synthesized by the reaction with HCl at 400"C'7,19. These are again accessible to insertion reactions, e.g., by electrointercalation2'. The compounds Liz[Mo6Se6] completely disperse in organic solvents like NMF, DMSO, and propylene carbonate; e.g., in DMSO the dispersed solid forms a viscous, burgundy red solution2'. Dispersions of Li2[Mo6Se6] can be prepared also by direct reaction of the indium compound with t-BuLi and extraction of the solid with DMSO". EXAFS studies of these solutions show that the structure of the [(Mo3Se3)]- is not disturbed significantly upon d i s s o l ~ t i o n ~ ~ . (A. LERF)
1. A. Meerschaut, J. Rouxel, in Crystal Chemistry and Properties of Materials with Quasi-OneDimensional Structures, J. Rouxel, ed., Reidel, Dordrecht, 1986. 2. R. R. Chianelli, M. B. Dines, Inorg. Chem., 14, 2417 (1975). 3. D. W. Murphy, F. A. Trumbore, J . Cryst. Growth, 39, 185 (1977). 4. C. Sourisseau, S. P. Gwet, P. Gard, Y. Mathey, J . Solid State Chem., 72, 257 (1988). 5. M. S. Whitingham, Prog. Solid State Chem., I Z , 71 (1978). 6. E. Canadell, C. Thieffry, Y. Mathey, M.-H. Whangbo, Inorg. Chem., 28, 3043 (1989). 7. C. Sourisseau, N. Allali, M. Danot, Eur. J . Solid State Inorg. Chem., 29, 111 (1992). 8. A. Leblanc, M. Danot, S. Benazeth, H. Dexpert, Eur. J . Solid State Inorg. Chem., 27, 725 (1990). 9. A. J. Jacobson, in Comprehensice Supramolecular Chemistj, Vol. 7, G. Alberti, T. Bein, eds., Pergamon Press, Oxford, 1996. 10. H. Boller, Monatsh. Chern., 109, 975 (1978). 11. H. O'Daniel, Z . Kistallogr., 86, 192 (1933). 12. H. Blaha, H. Boller, Monatsh. Chem., 111, 475 (1980). 13. P. Taylor, D. W. Shoesmith, Can. J . Chem., 56, 2797 (1978). 14. H. Boller, H. Blaha, Monatsh. Chem., 113, 145 (1983). 15. A. J. Jacobson, M. S. Whitingham, S. M. Rich, J . Electrochem. Soc., 126, 887 (1979). 16. A. J. Jacobson, L. E. McCandlish, J . Solid State Chem., 29, 355 (1979). 17. R. Chevrel, M. Sergent, in Crystal Chemistry and Properties of Materials with Quasi-OneDimensional Structures, J. Rouxel, ed., Reidel, Dordrecht 1986.
292
18. 19. 20. 21.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.4. Framework Structures 3.1 1.6.4.1. Structures with One-Dimensional Channels
J. M. Tarascon, G . W. Hull, F. J. DiSalvo, Mater. Res. Bull., 19, 915 (1984). M. Potel, P. Gougeon, R. Chevrel, M. Sergent, Rev. Chim. Miner., 21, 509 (1984). J. M. Tarascon, Solid State Ionics, 18 and 19, 802 (1986). J. M. Tarascon, F. J. DiSalvo,C. H. Chen, P. J. Carroll, M. Walsh, L. Rupp, J . Solid State Chem.,
58, 290 (1985). 22. J. H. Golden, F. J. DiSalvo, J. M. J. Frechet, Chem. Mater., 6, 844 (1994). 23. D. A. Holtman, B. K. Teo, J. M. Tarascon, B. A. Averill, Inorg. Chem., 26, 1669 (1987).
3.1 1.6.4. Framework Structures 3.1 1.6.4.1. Structures with One-Dimensional Channels
(i) Nb3X4and Related Compounds. The crystal structure of Nb,X, (X = S, Se, Te) is described as a three-dimensional network of distorted MX, octahedra (edge-and faceshared) with large hexagonal channels running parallel to the crystallographic c-axis'. In addition, there are several ternary phases A,M,X, (X = S, Se) of the early 3d transition metals (M = Ti and V) in which the framework is isostructural with that of the binary N b The homogeneity compound but the channels are occupied by T1 and K ranges of these phases are known for only a few cases and are not always fully established, e.g., in T1,V,S8 different homogeneity ranges are given ranging from 0.05 < x < 0.85 to 0.5 < x < 0.85,. The N b compounds (X = S, Se) are transferred to ternary phases by thermal reactions (high temperature reaction of TlSe/Se/Nb mixtures3 or ternary element insertion (In, Cu, Ag, Zn, Cd)' or by electrochemical intercalation' in aqueous salt solutions at RT. The ions inserted by electrointercalation are Li, Na, K, Ca: The intercalate content corresponds to a charge transfer of about 0.2 e-/Nb3X4'. N o uptake f solvent molecules was observed. New ternary phases A,[Nb&] (with A = Na, K, Rb, Cu, Ag, Pb) have been prepared also by an ion exchange reaction of T1,[Nb,X8] with the corresponding metal halide melts and simultaneous volatilization of the T1 halides, e.g. reaction of hz[MO&] in 3.1 1.6.3)'. In the ternary phases it is possible to remove the third element from the channels4~'-". The success of this procedure depends on the homogeneity ranges and the type of intercalate. In T1,V6S8, the T1 can be removed to a residual content of x = 0.2499, whereas in the corresponding K compound all ions can be removed to form the phase V3S4'0. The difference could be due to the covalent bonding of T1 to the host lattice6,'. These deintercalation reactions can be carried out electrochemically, by chemical oxidation with iodine/MeCN or just by HzO. The TisSee takes up HzO if exposed to HzO vapor up to a composition (HzO)l,5Ti6Se811.The empty host lattices are again susceptible to taking up metals in the channels; this is shown only for V6SS4. (ii) A,M,X,. The structure of TIVsSs, the prototype compound showing this structure, is that of a three-dimensional network of VX, octahedra sharing edges and faces. The connection pattern leads to formation of approximately rectangular one-dimensional channels running parallel to the crystallographic b axis". These channels accommodate the T1 atoms. A large number of isostructural compounds A,M5Xs (A = Na, K, Rb, Cs, In, T1; M = Ti, V, Cr, X = S, Se) have been ~ r e p a r e d ' The ~ . T1 atoms are removed from the channels by anodic oxidation', by oxidation with an aqueous FeCl, solution', or by oxidation with i ~ d i n e / M e C N ' ~ down . ' ~ to the lower limit of the homogeneity range of x = 0.33. Below this, the lattice collapses and V5Ss is f ~ r m e d l ~ However, ,'~. it is not quite clear whether the negative charges have been taken away from the guest ions, changing their oxidation state from Tl' to T13+9or from the host l a t t i ~ e ' ~ ' ' ~(the -'~
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
292
18. 19. 20. 21.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.4. Framework Structures 3.1 1.6.4.1. Structures with One-Dimensional Channels
J. M. Tarascon, G . W. Hull, F. J. DiSalvo, Mater. Res. Bull., 19, 915 (1984). M. Potel, P. Gougeon, R. Chevrel, M. Sergent, Rev. Chim. Miner., 21, 509 (1984). J. M. Tarascon, Solid State Ionics, 18 and 19, 802 (1986). J. M. Tarascon, F. J. DiSalvo,C. H. Chen, P. J. Carroll, M. Walsh, L. Rupp, J . Solid State Chem.,
58, 290 (1985). 22. J. H. Golden, F. J. DiSalvo, J. M. J. Frechet, Chem. Mater., 6, 844 (1994). 23. D. A. Holtman, B. K. Teo, J. M. Tarascon, B. A. Averill, Inorg. Chem., 26, 1669 (1987).
3.1 1.6.4. Framework Structures 3.1 1.6.4.1. Structures with One-Dimensional Channels
(i) Nb3X4and Related Compounds. The crystal structure of Nb,X, (X = S, Se, Te) is described as a three-dimensional network of distorted MX, octahedra (edge-and faceshared) with large hexagonal channels running parallel to the crystallographic c-axis'. In addition, there are several ternary phases A,M,X, (X = S, Se) of the early 3d transition metals (M = Ti and V) in which the framework is isostructural with that of the binary N b The homogeneity compound but the channels are occupied by T1 and K ranges of these phases are known for only a few cases and are not always fully established, e.g., in T1,V,S8 different homogeneity ranges are given ranging from 0.05 < x < 0.85 to 0.5 < x < 0.85,. The N b compounds (X = S, Se) are transferred to ternary phases by thermal reactions (high temperature reaction of TlSe/Se/Nb mixtures3 or ternary element insertion (In, Cu, Ag, Zn, Cd)' or by electrochemical intercalation' in aqueous salt solutions at RT. The ions inserted by electrointercalation are Li, Na, K, Ca: The intercalate content corresponds to a charge transfer of about 0.2 e-/Nb3X4'. N o uptake f solvent molecules was observed. New ternary phases A,[Nb&] (with A = Na, K, Rb, Cu, Ag, Pb) have been prepared also by an ion exchange reaction of T1,[Nb,X8] with the corresponding metal halide melts and simultaneous volatilization of the T1 halides, e.g. reaction of hz[MO&] in 3.1 1.6.3)'. In the ternary phases it is possible to remove the third element from the channels4~'-". The success of this procedure depends on the homogeneity ranges and the type of intercalate. In T1,V6S8, the T1 can be removed to a residual content of x = 0.2499, whereas in the corresponding K compound all ions can be removed to form the phase V3S4'0. The difference could be due to the covalent bonding of T1 to the host lattice6,'. These deintercalation reactions can be carried out electrochemically, by chemical oxidation with iodine/MeCN or just by HzO. The TisSee takes up HzO if exposed to HzO vapor up to a composition (HzO)l,5Ti6Se811.The empty host lattices are again susceptible to taking up metals in the channels; this is shown only for V6SS4. (ii) A,M,X,. The structure of TIVsSs, the prototype compound showing this structure, is that of a three-dimensional network of VX, octahedra sharing edges and faces. The connection pattern leads to formation of approximately rectangular one-dimensional channels running parallel to the crystallographic b axis". These channels accommodate the T1 atoms. A large number of isostructural compounds A,M5Xs (A = Na, K, Rb, Cs, In, T1; M = Ti, V, Cr, X = S, Se) have been ~ r e p a r e d ' The ~ . T1 atoms are removed from the channels by anodic oxidation', by oxidation with an aqueous FeCl, solution', or by oxidation with i ~ d i n e / M e C N ' ~ down . ' ~ to the lower limit of the homogeneity range of x = 0.33. Below this, the lattice collapses and V5Ss is f ~ r m e d l ~ However, ,'~. it is not quite clear whether the negative charges have been taken away from the guest ions, changing their oxidation state from Tl' to T13+9or from the host l a t t i ~ e ' ~ ' ' ~(the -'~
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.4. Framework Structures 3.1 1.6.4.2. Structures with a Three-Dimensional Net of Channels
293
metal atoms as well as the chalcogenide ions could be involved). The electronic structure of T1,V& seems to be rather peculiar. In contrast to TlxV&, the T1 can be removed to a lower limit of x = 0.07 in T1,Cr&13. A complete oxidative extraction of the third element is possible in NaCrjSe8l8. Upon cathodic reduction, Li can be inserted in “v5s8”4. Considering the residual T1, the compound obtained by lithiation should be written Ti0.3&ixV5S8. (A. LERF)
1. K. Selte, A. Kjekshus, Acta Crystallogr., 17, 1568 (1964). 2 .M. Vlasse, L. Fournes, Muter. Res. Bull., I I , 1527 (1976). 3. H. Boller, K. Klepp, Muter. Res. Bull., 18, 437 (1983). 4. R. Schollhorn, W. Schramm, D. Fenske, Angew. Chem., Int. Ed. Engl., 19, 492 (1980). 5. T. Ohtani, S. Onoue, Muter. Res. Bull., 21, 69 (1986). 6. R. Schlogl, W. Bensch, J . Less-Common Met., 132, 155 (1987). 7. G. Huan, M. Greenblatt, Muter. Res. Bull., 22, 505 (1987). 8. R. Schollhorn, W. Schramm, 2. Naturforsch. Teil B, 34, 697 (1979). 9. R. Schollhorn, in Physics oflntercalation Compounds, vol. 38, L. Pietronero, E. Tosatti, eds., Springer Series in Solid-state Sciences, Springer-Verlag, Berlin, 1981. 10. W. Bensch, J. Koy, Acta Crystallogr., Sect. C, 49, 1133 (1993). 11. W. Bensch, J. Koy, T. Braun, P. Hug, Solid State lonics, 74, 141 (1994). 12. L. Fournes, M. Vlasse, M. Saux, Muter. Res. Bull., 12, l(1977). 13. W. Bensch, 0. Helmer, C. Nather, J . Solid State Chem., 127, 40 (1996). 14. T. Ohtani, S. Onoue, J . Solid State Chem., 59, 324 (1985). 15. W. Bensch, E. Worner, Solid State lonics, 58, 275 (1992). 16. H. Nishihara, T. Ohtani, S. Onoue, Europhys. Lett., 8, 189 (1989). 17. W. Bensch, E. Worner, M. Muhler, U. Ruschewitz, Eur. J . Solid State Inorg. Chern., 30, 645 (1993). 18. T. Ohtani, Y. Sano, K. Kodoma, S. Onoue, H. Nishihara, Muter. Res. Bull., 28, 501 (1993). 3.1 1.6.4.2. Structures with a Three-Dimensional Net of Channels
(i) Sulfide Spinel. A range of stoichiometry (0.6 < x < 1) was found for the spinel Cu[Ti12S4 crystals grown by iodine vapor transport’. By oxidation with an aqueous solution of FeC1, or by anodic oxidation in aprotic Cu’+ electrolyte, this range can be extended to 0 < x < 1’. The structure of the spinel is retained during the course of this reaction, leading to the new metastable titanium disulfide with a cubic structure, henceforth called c-TiS,. At temperatures higher than 420°C this compound undergoes a phase transition to the hexagonal layered structure. The following reaction cycle can be carried out: deintercalation of the spinel to c-TiS2 transformation to h-TiS2,Cu intercalation to Cuo.sTiS,, heating to 330°C to the recovery of the spinel3. The spinel phase occurs over a stoichiometry range in Ti and Cu with an overall range Cu,[Ti]2 +yS4, thus giving opportunity to prepare c-[Ti]2 +yS44. Oxidation can also be carried out by bromine or iodine in MeCN at RT or by iodine at elevated temperature (cf. gas phase transport leading to a homogeneity r a ~ ~ g e The ) ~ , lower ~ . limit of the Cu content amounts to x = 0.07 unless the sample has an slight excess of Ti4. This cubic phase takes up lithium to form L ~ , C U ~ . ~ ~ with [ T ~large ] ~ Shomogeneity ~ range extended from x = 0 to x = 24,’. Lithiation can be carried out by the BuLi method and electrochemically4. Lithium ions occupy octahedral sites irrespective of the Li content’. (ii) Chevrel Phases A,.Mo,X,. The basic huilding blocks of A,Mo6X8 are Mo octahedra sourrounded by eight chalcogen atoms forming a cube (chalcogen atoms are located above the triangular sites of the octahedra). These cubes are tilted toward each
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.1 1.6 By Insertion Reactions from Solutions 3.1 1.6.4. Framework Structures 3.1 1.6.4.2. Structures with a Three-Dimensional Net of Channels
293
metal atoms as well as the chalcogenide ions could be involved). The electronic structure of T1,V& seems to be rather peculiar. In contrast to TlxV&, the T1 can be removed to a lower limit of x = 0.07 in T1,Cr&13. A complete oxidative extraction of the third element is possible in NaCrjSe8l8. Upon cathodic reduction, Li can be inserted in “v5s8”4. Considering the residual T1, the compound obtained by lithiation should be written Ti0.3&ixV5S8. (A. LERF)
1. K. Selte, A. Kjekshus, Acta Crystallogr., 17, 1568 (1964). 2 .M. Vlasse, L. Fournes, Muter. Res. Bull., I I , 1527 (1976). 3. H. Boller, K. Klepp, Muter. Res. Bull., 18, 437 (1983). 4. R. Schollhorn, W. Schramm, D. Fenske, Angew. Chem., Int. Ed. Engl., 19, 492 (1980). 5. T. Ohtani, S. Onoue, Muter. Res. Bull., 21, 69 (1986). 6. R. Schlogl, W. Bensch, J . Less-Common Met., 132, 155 (1987). 7. G. Huan, M. Greenblatt, Muter. Res. Bull., 22, 505 (1987). 8. R. Schollhorn, W. Schramm, 2. Naturforsch. Teil B, 34, 697 (1979). 9. R. Schollhorn, in Physics oflntercalation Compounds, vol. 38, L. Pietronero, E. Tosatti, eds., Springer Series in Solid-state Sciences, Springer-Verlag, Berlin, 1981. 10. W. Bensch, J. Koy, Acta Crystallogr., Sect. C, 49, 1133 (1993). 11. W. Bensch, J. Koy, T. Braun, P. Hug, Solid State lonics, 74, 141 (1994). 12. L. Fournes, M. Vlasse, M. Saux, Muter. Res. Bull., 12, l(1977). 13. W. Bensch, 0. Helmer, C. Nather, J . Solid State Chem., 127, 40 (1996). 14. T. Ohtani, S. Onoue, J . Solid State Chem., 59, 324 (1985). 15. W. Bensch, E. Worner, Solid State lonics, 58, 275 (1992). 16. H. Nishihara, T. Ohtani, S. Onoue, Europhys. Lett., 8, 189 (1989). 17. W. Bensch, E. Worner, M. Muhler, U. Ruschewitz, Eur. J . Solid State Inorg. Chern., 30, 645 (1993). 18. T. Ohtani, Y. Sano, K. Kodoma, S. Onoue, H. Nishihara, Muter. Res. Bull., 28, 501 (1993). 3.1 1.6.4.2. Structures with a Three-Dimensional Net of Channels
(i) Sulfide Spinel. A range of stoichiometry (0.6 < x < 1) was found for the spinel Cu[Ti12S4 crystals grown by iodine vapor transport’. By oxidation with an aqueous solution of FeC1, or by anodic oxidation in aprotic Cu’+ electrolyte, this range can be extended to 0 < x < 1’. The structure of the spinel is retained during the course of this reaction, leading to the new metastable titanium disulfide with a cubic structure, henceforth called c-TiS,. At temperatures higher than 420°C this compound undergoes a phase transition to the hexagonal layered structure. The following reaction cycle can be carried out: deintercalation of the spinel to c-TiS2 transformation to h-TiS2,Cu intercalation to Cuo.sTiS,, heating to 330°C to the recovery of the spinel3. The spinel phase occurs over a stoichiometry range in Ti and Cu with an overall range Cu,[Ti]2 +yS4, thus giving opportunity to prepare c-[Ti]2 +yS44. Oxidation can also be carried out by bromine or iodine in MeCN at RT or by iodine at elevated temperature (cf. gas phase transport leading to a homogeneity r a ~ ~ g e The ) ~ , lower ~ . limit of the Cu content amounts to x = 0.07 unless the sample has an slight excess of Ti4. This cubic phase takes up lithium to form L ~ , C U ~ . ~ ~ with [ T ~large ] ~ Shomogeneity ~ range extended from x = 0 to x = 24,’. Lithiation can be carried out by the BuLi method and electrochemically4. Lithium ions occupy octahedral sites irrespective of the Li content’. (ii) Chevrel Phases A,.Mo,X,. The basic huilding blocks of A,Mo6X8 are Mo octahedra sourrounded by eight chalcogen atoms forming a cube (chalcogen atoms are located above the triangular sites of the octahedra). These cubes are tilted toward each
294
3.1 1.6 By Insertion Reactions from Solutions 3.11.6.4. Framework Structures 3.1 1.6.4.2. Structures with a Three-Dimensional Net of Channels
other such that the molybdenum atoms of one cube can take up bonding interactions with the chalcogen atoms of the sourrounding cubes. Thus a three-dimensional framework is formed which contains intersecting vacant diffusion channels. In the ternary compounds, the A metals are distributed over these interstitial sites; A can be an alkali metal, an alkaline earth metal, a 3d element, a posttransition element (e.g., Ag, In, Sn Pb), a rare earth or an actinide; x is determined by the valence of the metal and the maximum electron uptake of the electron-deficient clusters. This is 4 e-/Mo6X8, thus leading to an upper limit of the anion network excess charge corresponding to [ M o , X , ] ~ - ~ .For X = Se and Te the metal-free binaries exhibiting the same structural framework can be obtained by thermal reactions; but the corresponding sulfide cannot be stabilized at high temperature without metals. It can be prepared as a metastable compound by leaching out the metal Ni,Mo,X, or Cu2M06X8' with HCI. This oxidative deintercalation also can be carried out electrochemically' in aqueous or nonaqueous electrolytes. Reversal of this reaction-the electrochemical intercalation-is also possible. The following ions can be inserted at RT into the binary chalcogenides Mo6X8 with X = S and Se93". at: Li', Na', M n 2 + , Fe2+, Co", N i 2 + , Cu', Ag', Z n 2 + , C d 2 + . The intercalation/deintercalation processes are fully reversible; there is no single homogeneity range in the electron transfer domain 0 < n < 4. The number of intermediate phases and extent of their homogeneity ranges depend on the metal to be intercalated, e.g. with Cu there are two phases, one with a very narrow homogeneity range at x 1 and the second with a very broad homogeneity range: 1.8 < x < 4'. This interpretation is in better agreement with data obtained for thermally prepared samples' ', but this would mean that the electrochemical potential curve shows additional features due to ion rearrangements. In the course of Li intercalation in Mo6X' with X = S and Se, the existence of three phases is clearly established: Li,Mo,X,, Li,Mo,X,, and Li&fO&. Whereas the first and the last are characterized by full electron transfer and the presence of lithium ions, the intermediate phase shows rather peculiar features, which have been interpreted with the formation of Li metal clusters'2. If divalent ions like Zn or Cd are intercalated, two phases form: Zn,Mo6X, (Cd,Mo,X,) and Zn,Mo,X, and Cd,Mo,Se8. Formation of the corresponding Cd2M06S8seems to be prevented by the size of the cationI3. Intercalation of Ni2' in Mo6& from aprotic solvents leads first to formation of Ni,Mo6SE, which homogeneously absorbs Ni up to x = 2; however, in an aqueous solution 6 e-/MO,& are transferred to the solid. In the first step of the reaction the empty host lattice and NilMo6S8 coexist, whereas at n = 2 e-/Mo6S8 a cointercalation of Ni2' and protons occurs14. It has been assumed that hydrogen-bridged binuclear Ni clusters have been formed ". In the few It is also possible to obtain phases with two cointercalated metal pseudoternary systems studied up to nOw-Li,CU,M0,&'5 and Li,CU,MO&,'6-the regions of full miscibility are rather small, and extended domains of two- and three-phase mixtures appears in the ternary phase diagrams at room temperature. The chalcogenide anions of Mo&' can be partially replaced by halide ions. This reduces the electron deficieny of the Mo6 clusters; maximum uptake of metal ions should decrease, and in fact investigations on the systems Li,Mo6Ses and Na,MO& -yIy (with X = S, Se)" show that the upper limit x for Li uptake is reduced with increasing y value. It is also possible to replace some of the Mo atoms by other metal atoms (e.g., Ru), and this affects the electron density of the Mo6 clusters. Since the reversible Li uptake in Li,[Mo~-,Ru,Se,] is not influenced by this substitution, it is concluded that ionic rather than electronic factors control the upper limit of the stoichiometry".
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3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 295 3.11.7 By Reactions in Melts
(iii) A,MolsX19. In this compound Mo,X, coexists with the smallest condensed cluster Mo9Xll, which has a center of two face-sharing Mo, octahedral clusters. Stacking of these units creates different types of channels: e.g., zigzag channels in In 3Mo15Se19 and intersecting channels in In2Mol5Sel9like that found in the Chevrel phases”. The isostructural sulfide compound In. 3.5M015S19 has been obtained alsoz1. As with A2M06X, it is possible to remove the In atoms by treatment with HCI at about 400°C and to obtain the metastable binaries Mo15X1920’21.With the Se compound both crystallographic forms can be retained in the binariesz2.These binaries can be loaded again with several metal atoms. Lithium (also by reaction with BuLi) and Na can be inserted electrochemically (in nonaqueous electrolytes) at ambient temperature. Up to eight Li atoms can be inserted in the Se compounds in a sequence of singleand two-phase regions whose extent depends on the structural modification2’. Sodium can be inserted also to a maximum content of x = 8, but the uptake is reversible only up to x = 3.5 and x = 2 for the two different structural forms (cf. the Incontent of the starting material^)'^. Alkali metals have been intercalated in to the sulfide by ion exchange reactions from fused halide melts at elevated temperatures (see 3.1 1.6.3)”. In this case the alkali metal content does not exceed the metal content of the starting material In. 3.5Mo15S1g2’.The metals Zn, Cd, Sn, and T1 can be intercalated into the binary MolsSlg by thermal reactions at moderate temperatures”.
-
(A. LERF)
1. N. LeNegard, G. Collin, 0. Gorochov, Mater. Res. Bull., 10, 1279 (1975). 2. R. Schollhorn, A. Payer, Angew. Chem., Int. Ed. Engl., 24, 67 (1985). 3. R. Schollhorn, in Chemical Reactions in Organic and Inorganic Constrained Systems, R. Setton, ed., NATO AS1 Series C 165, Reidel, Dordrecht (1986). 4. 9. Sinha, D.W. Murphy, Solid State lonics, 20, 81 (1986). 5. A. C. W. P. James, J. B. Goodenough, N. J. Clayden, J . Solid State Chem., 77, 356 (1988). 6. R. Chevrel, M. Sergent, in Superconductivity in Ternary Compounds, Vol. 1, 0. Fischer, M. P. Maple, eds., Springer-Verlag, Berlin, 1982. 7. R. Chevrel, M. Sergent, J. Prigent, Muter. Res. Bull., 9, 1487 (1974). 8. R. Schollhorn, M. Kiimpers, J.O. Besenhard, Muter, Res. Bull., 12, 781 (1977). 9. R. Schollhorn, Angew, Chem., 92, 1015 (1980). 10. R. Schollhorn, in Inclusion Compounds, Vol. 1, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, eds., Academic Press, London, 1984. 11. R. Fliikiger, R. Baillif, J. Muller, K. Yvon, J . Less-Common Met., 72, 193 (1980). 12. E. Gocke, R. Schollhorn, G. Aselman, W. Miiller-Warmuth, Inorg. Chem., 26, 1805 (1987). 13. E. Gocke, W. Schramm, P. Dolscheid, R. Schollhorn, J . Solid State Chem., 70, 71 (1987). 14. W. Schramm, E. Gocke, R. Schollhorn Muter. Res. Bull., 21, 929 (1986). 15. W. R. McKinnon, J. R. Dahn, C. C. H. Jui, J . Phys. C , Solid State Phys., 18, 4443 (1985). 16. L. S. Selvyn, W. R. McKinnon, J . Phys. C , Solid State Phys., 21, 1905 (1988). 17. L. W. ter Haar, F. J. DiSalvo, Phys. Rev. B, 34, 7342 (1986). 18. J. M. Tarascon, G. W. Hull, P. Marsh, L. W. ter Haar, J . Solid State Chem., 66, 204 (1987). 19. L. S. Selvyn, W. R. McKinnon, J . Phys. C., Solid State Phys., 20, 5105 (1987). 20. R. Chevrel, M. Sergent, in Crystal Chemistry and Properties of Materials with Quasi-OneDimensional Structures, J. Rouxel, ed., Reidel, Dordrecht, 1986. 21. J. M. Tarascon, G. W. Hull, Mater, Res. Bull., 21, 859 (1986). 22. J. M. Tarascon, D. W. Murphy, Phys. Rev. B, 33, 2625 (1986). 23. J. M. Tarascon, Solid State lonics, 18 and 19, 768 (1986).
3.11.7 By Reactions in Melts Reactions by melts are used primarily in preparation of binary and ternary chalcogenides containing alkali or alkaline earth metals. Closed or open systems can be used,
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 295 3.11.7 By Reactions in Melts
(iii) A,MolsX19. In this compound Mo,X, coexists with the smallest condensed cluster Mo9Xll, which has a center of two face-sharing Mo, octahedral clusters. Stacking of these units creates different types of channels: e.g., zigzag channels in In 3Mo15Se19 and intersecting channels in In2Mol5Sel9like that found in the Chevrel phases”. The isostructural sulfide compound In. 3.5M015S19 has been obtained alsoz1. As with A2M06X, it is possible to remove the In atoms by treatment with HCI at about 400°C and to obtain the metastable binaries Mo15X1920’21.With the Se compound both crystallographic forms can be retained in the binariesz2.These binaries can be loaded again with several metal atoms. Lithium (also by reaction with BuLi) and Na can be inserted electrochemically (in nonaqueous electrolytes) at ambient temperature. Up to eight Li atoms can be inserted in the Se compounds in a sequence of singleand two-phase regions whose extent depends on the structural modification2’. Sodium can be inserted also to a maximum content of x = 8, but the uptake is reversible only up to x = 3.5 and x = 2 for the two different structural forms (cf. the Incontent of the starting material^)'^. Alkali metals have been intercalated in to the sulfide by ion exchange reactions from fused halide melts at elevated temperatures (see 3.1 1.6.3)”. In this case the alkali metal content does not exceed the metal content of the starting material In. 3.5Mo15S1g2’.The metals Zn, Cd, Sn, and T1 can be intercalated into the binary MolsSlg by thermal reactions at moderate temperatures”.
-
(A. LERF)
1. N. LeNegard, G. Collin, 0. Gorochov, Mater. Res. Bull., 10, 1279 (1975). 2. R. Schollhorn, A. Payer, Angew. Chem., Int. Ed. Engl., 24, 67 (1985). 3. R. Schollhorn, in Chemical Reactions in Organic and Inorganic Constrained Systems, R. Setton, ed., NATO AS1 Series C 165, Reidel, Dordrecht (1986). 4. 9. Sinha, D.W. Murphy, Solid State lonics, 20, 81 (1986). 5. A. C. W. P. James, J. B. Goodenough, N. J. Clayden, J . Solid State Chem., 77, 356 (1988). 6. R. Chevrel, M. Sergent, in Superconductivity in Ternary Compounds, Vol. 1, 0. Fischer, M. P. Maple, eds., Springer-Verlag, Berlin, 1982. 7. R. Chevrel, M. Sergent, J. Prigent, Muter. Res. Bull., 9, 1487 (1974). 8. R. Schollhorn, M. Kiimpers, J.O. Besenhard, Muter, Res. Bull., 12, 781 (1977). 9. R. Schollhorn, Angew, Chem., 92, 1015 (1980). 10. R. Schollhorn, in Inclusion Compounds, Vol. 1, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, eds., Academic Press, London, 1984. 11. R. Fliikiger, R. Baillif, J. Muller, K. Yvon, J . Less-Common Met., 72, 193 (1980). 12. E. Gocke, R. Schollhorn, G. Aselman, W. Miiller-Warmuth, Inorg. Chem., 26, 1805 (1987). 13. E. Gocke, W. Schramm, P. Dolscheid, R. Schollhorn, J . Solid State Chem., 70, 71 (1987). 14. W. Schramm, E. Gocke, R. Schollhorn Muter. Res. Bull., 21, 929 (1986). 15. W. R. McKinnon, J. R. Dahn, C. C. H. Jui, J . Phys. C , Solid State Phys., 18, 4443 (1985). 16. L. S. Selvyn, W. R. McKinnon, J . Phys. C , Solid State Phys., 21, 1905 (1988). 17. L. W. ter Haar, F. J. DiSalvo, Phys. Rev. B, 34, 7342 (1986). 18. J. M. Tarascon, G. W. Hull, P. Marsh, L. W. ter Haar, J . Solid State Chem., 66, 204 (1987). 19. L. S. Selvyn, W. R. McKinnon, J . Phys. C., Solid State Phys., 20, 5105 (1987). 20. R. Chevrel, M. Sergent, in Crystal Chemistry and Properties of Materials with Quasi-OneDimensional Structures, J. Rouxel, ed., Reidel, Dordrecht, 1986. 21. J. M. Tarascon, G. W. Hull, Mater, Res. Bull., 21, 859 (1986). 22. J. M. Tarascon, D. W. Murphy, Phys. Rev. B, 33, 2625 (1986). 23. J. M. Tarascon, Solid State lonics, 18 and 19, 768 (1986).
3.11.7 By Reactions in Melts Reactions by melts are used primarily in preparation of binary and ternary chalcogenides containing alkali or alkaline earth metals. Closed or open systems can be used,
296
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.7 By Reactions in Melts 3.1 1.7.2 In Molten Salts
and the molten component may either participate in the reaction or serve as a flux'. Open systems typically have H2S or inert gases flowing over the reactants. An excellent review of these procedures, as they pertain to not only lanthanides and actinides but to transition metals, has been written2. (P. K. DORHOUT, H. STEINFINK)
1. M. G. Kanatzidis, Chem. Mater., 2, 353 (1990). 2. M. Guittard, J. Flahaut, in Synthesis of Lanthanide and Actinide Compounds, G. Meyer, L. R. Morss, eds., Kluwer, Dordrecht, 1991.
3.1 1.7.1 In Molten Metals
Weighed mixtures of elements sealed in evacuated silica tubes are heated for several days at 8OO0C, yielding the phases A,MX2, (A = Li, Na, K; M = Nb, Ta; X = S, Se; x = 0.6-0.7)'. The same phases form when metal dichalcogenides react with alkali metals. Various proportions of the elements Ge, Se, and Te are melted in evaculted, (0.65 < x < 0.85)2.Combisealed Vycor tubes, producing the solid solution GeSe,Te, -, nation of TiSz and Hg metal by mixing the solid with the liquid and heating in a sealed ampule for 2 days at 320°C yields superstoichiometric compounds, e.g., Hg1,,,TiSz3. A series of layered solids of formula M,PQ3 (M = Fe, Sn, In; x = 0.3333 or 0.6667; Q = S, Se) form from the elements in sealed silica ampules between 700 and 900°C in the presence of molten Q4,5.Metal-rich phases of early transition metal chalcogenides such as Ta6.08Nb4.92S4 also form in high frequency furnaces from the elements or by arcmelting the elements in a water-cooled hearth (generally with an excess of the more volatile metal)6. (P. K. DORHOUT, H. STEINFINK)
1. W. P. F. A. M. Omloo, F. Jellinek, J . Less-Common Met., 20, 121 (1970). 2. J. A. Muir, R. J. Cashman, J . Phys. Chem. Solids, 28, 1009 (1967). 3. E. W. Ong, M. J. McKelvy, G. Ouvrard, W. S. Glaunsinger, Chem. Mater., 4, 14 (1992). 4. W. Klingen, G. Eulenberger, H. Hahn, Naturwissenschaften, 55, 229 (1968). 5. A, Katty, S. Soled, A. Wold, Mater. Res. Bull., 12, 663 (1977). 6. X. Yao, H. F. Franzen, J . Solid State Chem., 86, 88 (1990).
3.11.7.2 In Molten Salts
Layered ternary sulfides of the form Ao.5MS2(A = Li, Cs) are obtained by means of alkali halide melts'.'. The dichalcogenide is mixed with a 10-fold molar excess of alkali halide in an alumina crucible; an H2S atmosphere is maintained by flowing gas over the reactants for a limited time during the overall reaction interval. The timing of the HzS flow is critical for the preparation, and the reaction temperature is maintained 50-1 50°C above the melting point of the halides (i.e., 750-950°C). Compounds Nao,5TiSzare also obtained using Ti or TiOz as the starting material, although reaction is slower than under H2S.It is impossible to prepare single-phase materials by reacting TaS2 with alkali halide melts and H2S.However, a single-phase Ao,3TaSzforms when the reaction is carried out under an inert atmosphere. Compounds Nao.5TiSz,Ko.55TiS2,and Lio,4TiSzalso form when TiS, reacts in salt melts of the corresponding halides at 900-1000°C in a stream of H2S/CSZ3.Reacting WS2 in a melt of LiBH4 at 350°C for 12 h yields Li,WSZ4. The phase K0.3Ti3S4is obtained when a 1 : 1.7 mixture of TiS, and K reacts at ca. 1000°C in molten KC15. Reduction of MoSz with alkali metals in KCl, RbCl, and CsCl
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
296
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.7 By Reactions in Melts 3.1 1.7.2 In Molten Salts
and the molten component may either participate in the reaction or serve as a flux'. Open systems typically have H2S or inert gases flowing over the reactants. An excellent review of these procedures, as they pertain to not only lanthanides and actinides but to transition metals, has been written2. (P. K. DORHOUT, H. STEINFINK)
1. M. G. Kanatzidis, Chem. Mater., 2, 353 (1990). 2. M. Guittard, J. Flahaut, in Synthesis of Lanthanide and Actinide Compounds, G. Meyer, L. R. Morss, eds., Kluwer, Dordrecht, 1991.
3.1 1.7.1 In Molten Metals
Weighed mixtures of elements sealed in evacuated silica tubes are heated for several days at 8OO0C, yielding the phases A,MX2, (A = Li, Na, K; M = Nb, Ta; X = S, Se; x = 0.6-0.7)'. The same phases form when metal dichalcogenides react with alkali metals. Various proportions of the elements Ge, Se, and Te are melted in evaculted, (0.65 < x < 0.85)2.Combisealed Vycor tubes, producing the solid solution GeSe,Te, -, nation of TiSz and Hg metal by mixing the solid with the liquid and heating in a sealed ampule for 2 days at 320°C yields superstoichiometric compounds, e.g., Hg1,,,TiSz3. A series of layered solids of formula M,PQ3 (M = Fe, Sn, In; x = 0.3333 or 0.6667; Q = S, Se) form from the elements in sealed silica ampules between 700 and 900°C in the presence of molten Q4,5.Metal-rich phases of early transition metal chalcogenides such as Ta6.08Nb4.92S4 also form in high frequency furnaces from the elements or by arcmelting the elements in a water-cooled hearth (generally with an excess of the more volatile metal)6. (P. K. DORHOUT, H. STEINFINK)
1. W. P. F. A. M. Omloo, F. Jellinek, J . Less-Common Met., 20, 121 (1970). 2. J. A. Muir, R. J. Cashman, J . Phys. Chem. Solids, 28, 1009 (1967). 3. E. W. Ong, M. J. McKelvy, G. Ouvrard, W. S. Glaunsinger, Chem. Mater., 4, 14 (1992). 4. W. Klingen, G. Eulenberger, H. Hahn, Naturwissenschaften, 55, 229 (1968). 5. A, Katty, S. Soled, A. Wold, Mater. Res. Bull., 12, 663 (1977). 6. X. Yao, H. F. Franzen, J . Solid State Chem., 86, 88 (1990).
3.11.7.2 In Molten Salts
Layered ternary sulfides of the form Ao.5MS2(A = Li, Cs) are obtained by means of alkali halide melts'.'. The dichalcogenide is mixed with a 10-fold molar excess of alkali halide in an alumina crucible; an H2S atmosphere is maintained by flowing gas over the reactants for a limited time during the overall reaction interval. The timing of the HzS flow is critical for the preparation, and the reaction temperature is maintained 50-1 50°C above the melting point of the halides (i.e., 750-950°C). Compounds Nao,5TiSzare also obtained using Ti or TiOz as the starting material, although reaction is slower than under H2S.It is impossible to prepare single-phase materials by reacting TaS2 with alkali halide melts and H2S.However, a single-phase Ao,3TaSzforms when the reaction is carried out under an inert atmosphere. Compounds Nao.5TiSz,Ko.55TiS2,and Lio,4TiSzalso form when TiS, reacts in salt melts of the corresponding halides at 900-1000°C in a stream of H2S/CSZ3.Reacting WS2 in a melt of LiBH4 at 350°C for 12 h yields Li,WSZ4. The phase K0.3Ti3S4is obtained when a 1 : 1.7 mixture of TiS, and K reacts at ca. 1000°C in molten KC15. Reduction of MoSz with alkali metals in KCl, RbCl, and CsCl
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
296
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 3.1 1.7 By Reactions in Melts 3.1 1.7.2 In Molten Salts
and the molten component may either participate in the reaction or serve as a flux'. Open systems typically have H2S or inert gases flowing over the reactants. An excellent review of these procedures, as they pertain to not only lanthanides and actinides but to transition metals, has been written2. (P. K. DORHOUT, H. STEINFINK)
1. M. G. Kanatzidis, Chem. Mater., 2, 353 (1990). 2. M. Guittard, J. Flahaut, in Synthesis of Lanthanide and Actinide Compounds, G. Meyer, L. R. Morss, eds., Kluwer, Dordrecht, 1991.
3.1 1.7.1 In Molten Metals
Weighed mixtures of elements sealed in evacuated silica tubes are heated for several days at 8OO0C, yielding the phases A,MX2, (A = Li, Na, K; M = Nb, Ta; X = S, Se; x = 0.6-0.7)'. The same phases form when metal dichalcogenides react with alkali metals. Various proportions of the elements Ge, Se, and Te are melted in evaculted, (0.65 < x < 0.85)2.Combisealed Vycor tubes, producing the solid solution GeSe,Te, -, nation of TiSz and Hg metal by mixing the solid with the liquid and heating in a sealed ampule for 2 days at 320°C yields superstoichiometric compounds, e.g., Hg1,,,TiSz3. A series of layered solids of formula M,PQ3 (M = Fe, Sn, In; x = 0.3333 or 0.6667; Q = S, Se) form from the elements in sealed silica ampules between 700 and 900°C in the presence of molten Q4,5.Metal-rich phases of early transition metal chalcogenides such as Ta6.08Nb4.92S4 also form in high frequency furnaces from the elements or by arcmelting the elements in a water-cooled hearth (generally with an excess of the more volatile metal)6. (P. K. DORHOUT, H. STEINFINK)
1. W. P. F. A. M. Omloo, F. Jellinek, J . Less-Common Met., 20, 121 (1970). 2. J. A. Muir, R. J. Cashman, J . Phys. Chem. Solids, 28, 1009 (1967). 3. E. W. Ong, M. J. McKelvy, G. Ouvrard, W. S. Glaunsinger, Chem. Mater., 4, 14 (1992). 4. W. Klingen, G. Eulenberger, H. Hahn, Naturwissenschaften, 55, 229 (1968). 5. A, Katty, S. Soled, A. Wold, Mater. Res. Bull., 12, 663 (1977). 6. X. Yao, H. F. Franzen, J . Solid State Chem., 86, 88 (1990).
3.11.7.2 In Molten Salts
Layered ternary sulfides of the form Ao.5MS2(A = Li, Cs) are obtained by means of alkali halide melts'.'. The dichalcogenide is mixed with a 10-fold molar excess of alkali halide in an alumina crucible; an H2S atmosphere is maintained by flowing gas over the reactants for a limited time during the overall reaction interval. The timing of the HzS flow is critical for the preparation, and the reaction temperature is maintained 50-1 50°C above the melting point of the halides (i.e., 750-950°C). Compounds Nao,5TiSzare also obtained using Ti or TiOz as the starting material, although reaction is slower than under H2S.It is impossible to prepare single-phase materials by reacting TaS2 with alkali halide melts and H2S.However, a single-phase Ao,3TaSzforms when the reaction is carried out under an inert atmosphere. Compounds Nao.5TiSz,Ko.55TiS2,and Lio,4TiSzalso form when TiS, reacts in salt melts of the corresponding halides at 900-1000°C in a stream of H2S/CSZ3.Reacting WS2 in a melt of LiBH4 at 350°C for 12 h yields Li,WSZ4. The phase K0.3Ti3S4is obtained when a 1 : 1.7 mixture of TiS, and K reacts at ca. 1000°C in molten KC15. Reduction of MoSz with alkali metals in KCl, RbCl, and CsCl
3.11 Formation of the Nonstoichiometric Sulfides, Selenides, and Tellurides 297 3.11.7 By Reactions in Melts 3.1 1.7.2 In Molten Salts
melts at ca. 1OOOT in Ar yields crystals of AxMo4S6(x % 0.3333)6.When the reaction time is extended, gray needles with composition K0.4M03S4and Rb0.4M03S4form. At lower temperatures, A,MoS2 forms. Reacting Nb3S4 with Na or K in the corresponding chloride melt at 800-1000°C in alumina under Ar yields Nao.18Nb3S4and Ko.18Nb3S47. Phases of M,K4Te3 (M = Ca, Sr; x = 0.6) form in reactions of MTe and Te metal in K2Te melts at 600-850°C in sealed silica ampules for 12 ha. When melted in a high frequency furnace at Ar pressures up to 10 MPa (100 bars), prereacted amounts of Cu, Mo, and S yield Cu,Mo6S8 phases. Equilibration of these phases at 269 K gives x = 1.75-1.85, and at 187 K, x = 3.1-3.39,'0. Lower temperature routes using copper chloride and Mo6S8 yield Cu,Mo6Sa at 240°C in a flow tube with a flow of N 2 . Metal sulfides are preferred because they do not introduce impurities". The substoichiometric rare earth chalcogenides are made by reacting rare earth halides with alkali chalcogenides in alkali chalcogenide fluxes". A series of LnQ, -, and LnTe3-, phases is made by reacting LnCl, with A2Q,, (n = 3,4, 5 ) in sealed, evacuated silica ampules at temperatures as low as 200°C. Similar reactions with A2S4/A2Se4 yielded mixed rare earth chalcogenides, (LnS)Seo 7 9 . Other nonstoichiometric rare earth chalcogenides include K2Ln2-,Sb4+,Sel2, (Ln = La, Ce, Pr, Gd, x z 0.3333), prepared in melts of K2Se4 at 700"C13. (P. K. DORHOUT, H. STEINFINK)
M. Schollhorn, M. Kiimpers, D. Plorin, J . Less-Common Met., 58, 55 (1978). R. Schollhorn, A. Lerf, J . Less-Common Met., 42, 89 (1975). R. Schollhorn, A. Weiss, Z. Naturforsch., Teil B , 28, 711 (1973). H. L. Tsai, J. Heising, J. L. Schindler, C. R. Kannewurf, M. G. Kanatzidis, Chem. Mater., 9, 879 (1997). 5. R. Schollhorn, W. Schramm, D. Fenske, Angew. Chem., Int. Ed. Engl., 19,492 (1980). 6. M. Kumpers, R. Schollhorn, Z. Naturforsch., Teil B , 28, 929 (1980). 7. R. Schollhorn, W. Schramm, Z. Naturforsch., Teil B , 34, 697 (1979). 8. I. Schewe-Miller, P. Bottcher, J . Alloys Compd., 183, 98 (1992). 9. R. Fliikiger, R. Baillif, E. Walker, Mater. Res. Bull., 13, 743 (1978). 10. R. Fliikiger, A. Junod, R. Bailiff, P. Spitzli, A. Treyvaud, A. Paoli, H. Devantay, J. Miiller, Solid State Commun.,23, 699 (1977). 11. P. Rabiller, M. Rabillerbaudry, S. Evenboudjada, L. Burel, R. Chevrel, M. Sergent, M. Decroux, J. Cors, J. L. Maufras, Mater. Res. Bull., 29, 567 (1994). 12. J. H. Chen, P. K. Dorhout, J . Solid State Chem., 117, 318 (1995). 13. J. H. Chen, P. K. Dorhout, J . Alloys Compd., 249, 199 (1997). 1. 2. 3. 4.
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
Abbreviations abs ax. Ac acac acacH AcO Ad ads AIBN Alk amt Am amu anhyd aq Ar asym at atm av BBN bcc BD BIMOP BINAP
bipy bipyH BMPP bP Bu Bz C-
ca. catal CDT cf. Ch. CHD Chx ChxD CI Cob COD COE
absolute alternating current acetyl, CH,CO acetylacetonate anion acetylacetone, CH,C(O)CH,C(O)CH, acetate anion, CH,C(O)O adamantyl adsorbed 2.2’-azobis(isobutyronitrile),2,2’-[(CH,),CCNl,NZ alkyl amount amyl, C5H,, atomic mass unit anhydrous aqueous aryl asymmetrical, asymmetric atom (not atomic, except in atomic weight) atmosphere (not atmospheric) average 9-Borabicyclo[3.3. Ilnonane body-centered cubic butadiene 6,6’-bis(diphenylphosphino)-3,3‘-dimethoxy-2,2’,4,4’tetramethyl-I ,1’-biphenyl 2,2’-bis(dipheny1phosphino)-1,l ’-binaphthyl 2,2’-bipyridyl protonated 2,2’-bipyridyl benzylmethylphenylphosphine,(PhCH,)(CH,)PhP boiling point butyl, C,H, benzyl, C,H,CH, cyclo (used in formulas) circa, about, approximately catalyst (not catalyzing, catalysis, catalyzed, etc.) cyclododecatriene compare chapter 1,3-cycloheptadiene c yclohexyl 1,3-~yclohexadiene configuration interaction cobalamine c y cloctadiene cyclooctene
299
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
300 conc const. COT COTe CP CPE CPm CT
cv
CVD CW CY d DABIP DBA d.c. DCM DCME DCP dct DDT dec DED depe DIAD diars dien diglyme dil diop
dipda diphos Div. DMA dme DME DMF DMG dmgh DMP dmpe DMSO dpam dpav dpic
Abbreviations concentrated (not concentration) constant cyclooctatriene c yclooctatetraene cyclopentadienyl, CSHJ controlled-potential electrolysis counts per minute charge-transfer cyclic voltammetry chemical vapor deposition continuous wave cyclohexyl, C,H,, day, days N,N’-diisopropyl- 1,4-diazabutadiene dibenzylideneacetone direct current dicyclopentadienylmethane CI,CHC(O)CH, 1,3-dicycIopentadienylpropane dithiocarbamato, [S2CNR,]dichlorodiphenyltrichloroethane, 1,1,1,’-trichloro-2,2-bis(4-chlorophenyl)ethane decomposed l,l-bis(ethoxycarbonyl)ethene-2,2-dithiolate, [[(HsC,OC(O)liC=CS,l’ 1,2-bis(diphenylphosphino)ethene, (C,H,),PCH=CHP(C6H,)2 diindenylanthracenyl 1 ,2-bis(dimethylarsino)benzeneIo-phenylenebis (dimethylarsine), 1,2-(CH,),AsC6H,As(CH,), diethylenetriamine, [H,N(CH,)J,NH diethyleneglycol dimethylether, CH,O(CH,CH,O)CH, dilute 2,3-O-isopropylidene-2,3-dihydroxy1,4bis(diphenylphophino)butane, (C,H,),PCH,CH[OCH(CH,)=CHZICH~]CH [OCH(CH,)=CH21CH,P(C,H,)z p-i-PrC,H,CH=CHC,H,-c-p 1,2-bis(diphenylphosphino)benzene,1,2(C,H,),PC,H4P(C,H,), division dimethylacetamide dropping mercury electrode 1,2-dimethoxyethane, glyme, CH,O(CH,),OCH, N,N-dimethylformamide, HC(O)N(CH,), dimethylglyoxime, CH,C(=NOH)C(=NOH)CH, dimethylglyoximate anion 1,2-dimethoxybenzene, 1 ,2-(CH,0),C,H4 1,2-bis(dimethyIphosphino)ethane, (CH,),P(CH,),P(CH,), dimethylsulfoxide, (CH,),SO bis (diphenylarsino)methane, [(C6H,),As12CH2 cis-l,2-bis(diphenylarsino)ethene,Ph,AsCH=CHAsPh? dipicolinate ion
Abbreviations DPP dPPb
DTA DTBQ DTH DTS ed. eds. edt EDTA e.g. EHMO emf en enH EPR equimol equiv EPR Eq. ERF ES ESR esu Et etc. Et,O EtOH et seq. eu fac Fc fcc ff. Fig F1 FP fP g g-at GLC glyme
differential pulse polarography 1,4-bis(diphenyIphosphino)butane,1,4(c6H,),p(cH,)4p(c6H,)2 1,2-bis(diphenyIphosphino)benzene,1 ,2-(Ph,P),C6H4 1,2-bis(diphenyIphosphino)ethane, 1,2(c6H,),p(cH,)2p(c6H,), 1,l-bis(diphenylphosphino)ethene, H,C=C(PPh,), bis(diphenylphosphino)methane, [(C,H,),Pl,CH, bis (dipheny1phosphoryl)ethane 1,3-bis(diphenylphosphino)propane,1,3(C~HJ),P(CHZ),P(C,H,)? 1,2-bis(di-p-toIylphosphino)ethane,1,2(~-CH,C,H~)LP(CH~),P(C~H~CH~-~)~ differential thermal analysis
3,5-di-t-butyl-o-benzoquinone
1,6-dithiahexane, butane-l,4-dithiol, 1,4-HS(CHJ4SH dithiosquarate edition, editor editors 1,2-ethanedithioIate ethylenediaminetetraacetic acid, [HOC(O)l~N(CH,),N[C(0)OHI~ exempli gratia, for example extended Hiickel molecular orbital electromotive force ethylenediamine, H2N(CH2),NH, protonated ethylenediamine electron paramagnetic resonance equimolar equivalent electron paramagnetic resonance equation effective reduction factor excited state electron-spin resonance electrostatic unit ethyl, CH,CH, et cetera, and so forth diethyl ether, (C,HJ20 ethanol, C,H,OH et sequentes, and the following entropy unit facial ferrocenyl face-centered cubic following figure fluorenyl qS-CSH,Fe(CO), freezing point gas gram-atom gas liquid chromatography 1,2-dimethoxyethane, CH,O(CH,),OCH,
301
302 graph GS h H-Cob HD hept Hex hfacac HMDB hmde MHI HMPA HOMO HPLC HPPK i.e. ImH inter alia IPC IR irrev ISC isn 1
L LC LF LFER liq LMCT Ln LSV LUMO m max M MC Me MeIm Me2Pn Men mes MeOH mer mhP min MLCT MO mol mP MV
Abbreviations graphite ground state hour, hours cobalamine 1,S-hexadiene heptyl hexyl 1,1,1,5,5,S-hexafluoro-2,4-pentanedione anion, CF,C(=O)CHC(=O)CF, hexamethyl(Dewar benzene) hanging mercury drop electrode heptamethylindenyl hexamethylphosphoramide [(CHJ2N1,PO highest occupied molecular orbital high-pressure liquid chromatography phenyl-2-p yri ylketoxime
id est, that is imidazole among other things isopinocarnphylborane infrared irreversible intersystem crossing isonicotinamide liquid ligand ligand centered ligand field linear free-energy relationship liquid ligand-to-metal charge transfer lanthanides, rare earths linear-scan voltammetry lowest unoccupied molecular orbital meta maximum metal metal centered methyl, CH, methylimidazole 2,2-dimethylpropane- 1,3-diamine, H,NCH2C(CHJ2CH2NH2 menthyl mesitylene, 1,3,5-trimethylbenzene derivative methanol, CH,OH meridional; the repeating unit of an oligomer or polymer 2-hydroxy-6-methylpyridine, 2-HO, 6-CH3C,H,N minimum, minute, minutes metal-to-ligand charge transfer molecular orbital molar melting point methyl viologen, 1,l '-dimethyl-4,4'-bipyridinium dichloride
Abbreviations n.a. naPY NBD neg nhe NMR N,n'-BzZen No. nP NP Nuc NPP NQR NTA 0
obs Oct OeP OEP 0, 0,
oq ox. P P. P Pat. pet. Ph phen Ph,PPy PPN PiP PMDT PMR Pn POS Po-tol, PP . PPb PPm PPn PPt Pr PSS PVC PY PYdac PYr PzH
not available naphth yridine norbornadiene, [2.2.1]bicyclohepta-2,5-diene negative normal hydrogen electrode nuclear magnetic resonance
N,N'-dibenzylethylenediamine, (C,H,CH,)HNCH,CH,NH(CH?C,H,)
number tris-[2-(diphenylphosphino)ethyl]amine, "CH,CHIP(C~H,)?I, naphthyl nucleophile normal pulse polarography nuclear quadrupole resonance nitrilotriacetate ortho observed octyl octaethylporphyrin octaeth ylporph yrin oxidation factor octahedral oxyquinolate oxidation para page pressure patent petroleum phenyl, C6H5 1,lo-phenanthroline 2-(diphenylphosphino)pyridine, 2-(C,H,),PC,H,N [(PhJ'hNI . ~ . piperidine, C,H,,N pentamethyldiethylenetriamine, (CH,),N(CH,),N(CH,)(CH2)2N(CH,)2 proton magnetic resonance propylene-l,3-diamine, 1 ,3-H,NCH2CH,CH2NH, positive tri-o-to1ylphosphine pages parts per billion parts per million bis(diphenylphosphino)amine, [(C,H,),P],NH precipitate ProPYL C,H, photostationary state poly(viny1 chloride) pyridine, C,H,N pyridine-2,6-dicarboxylate pyrazine pyrazol yl +
303
304 PZE rac R RDE RE red. Redox ref. rev rf RF RF rh rms rPm RT S
sal salen saldox sce SCE sec Sep Sia SMAD soh solv SP
STP sub1 Suppl. sym t T Td TACN TCNE TEA terPY tetrapho TGA TGL THF THP THT Thx TLC TMED tmen
Abbreviations potential of zero charge racemic mixture, racemate organic group; universal gas constant rotated disk electrode rare earths, lanthanides reduction reduction-oxidation reactions reference reversible radiofrequency reduction factor R group with substituted F rhombohedra1 root mean square revolutions per minutes room temperature second, seconds; solid salicylaldehyde N ,N’-bis(salicy1idene)ethylenediamine salicy laldoxime saturated calomel electrode standard calomel electrode secondary sepulcrate, 1,3,6,8,10,13,16,19octaazabicyclo[6.6.6]eicosane Diisoamyl solvated metal-atom dispersed solution solvated specific standard temperature and pressure sublimes supplement symmetrical, symmetric time; tertiary temperature tetrahedral 1,4,7-triazacycIononane tetrac yanoethylene tetraethylammonium ion, [(C,H,),N] 2,2’2”-terpyridyl +
Ph2PCH,CH2PPhCH2CH2PPhCH2CH2PPh2 thermogravimetric analysis triethyleneglycol dimethylether tetrahydrofuran detrah ydropyran tetrahydrothiophene thexyl thin-layer chromatography
N,N,N’,N’-tetramethylethylenediamine, (CHJ2N(CH2)P(CHA
N,N,N’,N’-tetramethylethylenediamine
305
Abbreviations TMP TMPH TMPP To1 Tos TPA TPP TPPO tren triars triphos trien TTP
uv
V
Vi viz. vol., Vol. VPE vs. wk. wt
X
xs
Y
Yr.
5
rl
2,2,6,6-tetramethylpiperidyl 2,2,6,64etramethylpiperidine, 2,2,6,6-(CH,),CSH,N tris(2,4,6-trimethoxyphenyl)phosphine tolyl, CbH,CH,, p-tolyl tosyl, tolylsulfonyl, 4-CH3C6H,SO2 tetraphenylarsonium ion, [(C,H,),As] tetraphenylprophyrin triphenylphosphineoxide tris(2-aminoethyl)amine, N(CH,CH,NH,), bis-[-(dimethylarsino)phenyl]methylarsine, [~-(CH,),ASC~H&ASCH, 1 ,1 ,1-tris(diphenylphosphinomethyl)ethane, [(C~HS)~PCHJ,CCH~ triethylenetetraamine, H,N(CH,),NH(CH2)2NH(CH2)2NH2 tetra-p-tolylporphrin ultraviolet vicinal (E)-[2-(CHj),NHC,C,H,IC=C(CHj)C,H,CH,-4 videlical, that is to say, namely volume vapor-phase epitaxy versus week weight halogen or pseudohalogen excess often used for S , Se year section hapto designator +
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
Author Index The entries of this index were derived directly by computer program from the lists of references. The accuracy of the references was the sole responsibility of the authors. No editorial check, except for format and journal-title abbreviation, was applied. Consequently, errors occurring in authors’ names in the references will recur in this index. Each entry in the index refers to the appropriate section number.
A
Abad, J.-A. 3.8.2.1.3 Abdulaev, G. B. 3.1.4.1.1 Abel, E. W. 3.8.3.6.3 Abrahams, I. L. 3.7.3.6 Abrahams, J. C. 3.10.3.3.1 Abrahams, S. C. 3.10.2.3.3 Adams, R. 3.7.3.6 Adams, R. W. 3.8.2.10.1 Adamson, A. W. 3.8.2.2.1 Adamson. G. W. 3.7.3.2 Adcock, D. 3.7.4.6.2.8 Addison, A. W. 3.7.3.3 Addison, C. C. 3.7.2.6.1 3.8.2.8.1 3.8.2.8.3 Adel, J. 3.8.4 Adkins, H.
3.8.2.10.1 Adler, P. 3.10.3.2.1.1 Adrian, H. 3.1 1.6.1.6 Agganval, S. L. 3.1.2.2.2 Agnus, Y. 3.1.2.1.2 Agrawal, M. M. 3.8.2.10.1 Ahrland, S. 3.7.2.4.1 Ainscough. E. W. 3.7.3.3 Airoldi, C. 3.7.2.4.1 Aitken, G. B. 3.7.4.6.2.7 Akashi, H. 3.8.3.6.1 3.8.3.6.3 Akerstrom, A 3.7.3.2 Akhundov, G. A. 3.7.4.1.1 Akiba, K. 3.7.4.6.2.9 Akiyama, M. 3.8.2.4.2 3.8.2.4.3 Akiyoshi, T.
3.7.4.1.1 3.7.4.1.2 Al-Akhdar, W. 3.8.2.1.3 Al-Ani. F. T. 3.8.3.6.2 Al-Kazzaz, Z . M. S. 3.8.2.6.1 Al-Khateeb. H. 3.8.2.1.2 Alberti, G. 3.11.6 3.11.6.1.1 3.1 1.6.1.7 3.11.6.3 Alberts, G. 3.11.6.2 Albrecht, N. 3.8.4 Albrecht-Schmitt, T. E. 3.8.3.6.2 3.8.4 Aleandre, L. E. 3.8.3.6.2 3.8.4 Aleksandrov. G. G. 3.8.3.6.3 Alekseevskii, V. B. 3.1.4.5 Alexandrov, Y. A. 3.7.2.1.3 Alexandrov. Yu. A.
307
308 Alexandrov, Yu. A. (Continued) 3.7.2.1.2 Alimov, M. Kh. 3.7.4.1.1 Allali, N. 3.11.6.3 Almond, M. 3.8.2.11.3 Alvey, P. J. 3.8.2.6.1 Amarasekera, J. 3.8.3.6.1 3.8.3.6.2 3.8.4 Amelinckx, S. 3.11.6.1.2 Amma. E. L. 3.7.3.3 Amundsen, A. R. 3.7.3.6 Andersen, A. F. 3.10.3.4 Andersen. R. A. 3.8.2.10.1 Anderson, B. B. 3.8.2.11.2 3.8.3.7.2 Anderson, D. L. 3.8.2.1.2 Anderson, J. S. 3.10.1.2.3 3.10.1.3.1 3.10.1.4.1 3.10.1.4.2 3.10.1.5.3 3.10.1.5.5 3.10.3.1.1 3.10.3.1.2 3.10.3.1.3 3.10.3.4 Anderson, S. 3.10.1.3.1 3.10.1.3.2 3.10.1.3.3 3.10.1.4.1 3.10.1.4.2 3.10.1.5.3 3.10.1.5.4 3.10.3.1.1 3.10.3.1.2 3.10.3.1.3 3.10.3.3.2 3.10.3.4.1 Andresen, A. F. 3.10.3.4.2
Author Index Andrews, L. 3.8.2.1.1 Andrews. L. J. 3.8.2.1.1 Angelici, R. J. 3.8.3.6.1 Angermaier, K. 3.7.3.6 Anne, M. 3.10.3.2.2.3 Ansari, M. A. 3.7.4.6.2.1 3.8.4 Anthony, A.-M. 3.10.3.1.3 Anthony, A. M. 3.10.1.2.3 Antipov, E. V. 3.10.3.2.1.2 3.10.3.3.1 Antonini, E. 3.8.2.1.2 Aoki, M. 3.7.4.1.1 3.7.4.1.2 Appelman, E. H. 3.9.2 3.9.4 Aragon, R. 3.10.2.2.1
Arasasingham, R. D. 3.8.2.1.3 Archer, R. D. 3.8.3.2.1 Archer, S. 3.8.2.7.1 Arcus. c. s. 3.7.2.1.2 Aresta, M. 3.8.2.1.3 Arkharov, V. I. 3.7.4.1.1 Arndt, R. 3.1 1.6.1.5 Arnold, A. P. 3.7.4.6.1.2 3.7.4.6.2.3 Arnold, E. 3.8.2.1.1 Arnold, Edward 3.7.2.1.1 Arnold, J. 3.7.4.6.2 3.1.4.6.2.4 3.7.4.7 3.8.3.6.2
Arnott, R. J. 3.10.3.2.4.3 Aselman, G. 3.11.6.4.2 Ashen, D. J. 3.7.4.7 Ashley-Smith. A. 3.8.2.6.1 Aslam, M. 3.7.3.6 Atsumi, T. 3.10.2.3.1 Atwood, J. L. 3.11.6. 3.11.6.1.2 3.11.6.1.6 3.11.6.4.2 Atynski, K. 3.7.4.1.1 3.7.4.2.1 3.7.4.3 Audiere, J. P. 3.11.6.2 Auken, I. 3.7.3.3 Auriel, C. 3.11.6.1.4 Aurivillius, B. 3.10.3.2.1.3 Aven, M. 3.7.4.1.1 3.7.4.1.2 Averill. B. A. 3.11.6.3 Avrorin. V. V. 3.9.4 Aylett, B. J. 3.7.4.2.1 Aylett, B. Z. 3.7.4.3 3.7.4.5 Aymes, D. 3.8.2.1.2
B
Bable, D. 3.10.3.5 Bachman, R. E. 3.8.4 Baenziger. N. C. 3.7.3.1.2 3.7.3.2 3.7.3.6 3.8.3.2.1 Baggio, R. F. 3.7.3.3
309
Author Index Baggio, S. 3.7.3.3 Baghlaf, k 0. 3.8.2.6.3 Bagnall, K. W. 3.8.2.6.1 Bagshaw, k N. 3.10.1.3.1 3.10.1.3.2 3.10.1.3.3 3.10.1.4.2 3.10.3.1.1 3.10.3.1.2 3.10.3.4.1 Bailar, J. G. 3.8.2.10.1 Bailey, M. G. 3.11.5.1 Bailey, N. k 3.7.3.6 Bailey, T. D. 3.7.3.6 Bailif, R. 3.11.6.4.2 3.11.7.2 Baillie, M. J. 3.8.2.10.1 Balasubramanian, k 3.8.3.2.1 3.8.3.6.3 Balch, A L. 3.8.2.1.3 Baldus, J. 3.8.3.4.2 Baldwin, F. E. 3.8.2.2.1 Balter, S . 3.7.4.6.2.4 Balthis, J. H. 3.8.2.10.1 Banda, R. M. H. 3.8.4 Bando, Y. 3.10.3.3.2 Banks, E. 3.10.3.2.4.1 3.10.3.3.4 Banoch. M. F. 3.7.4.2.1 3.7.4.3 Banus, M. D. 3.10.1.5.2 Bao, X 3.7.2.1.1 Baral, S. 3.1 1.5.1
Baranwal, B. P. 3.8.2.4.1 Barker, J. 3.10.3.2.2.3 3.10.3.2.4.5 Barnard, D. 3.7.4.6.2.5 Bartlett, N. 3.9.1 3.9.3 Basak, A. K. 3.8.2.1.3 Bashkin, J. K. 3.8.3.6.1 Basikhin, Yu. V. 3.8.2.4.2 Basolo, F. 3.8.2.1.2 3.8.2.2.1 3.8.2.9.1 Bass, K. C. 3.7.2.1.3 Batchelor, R. L. 3.1 1.6.2 Batlogg. B. 3.10.3.2.1.1 3.11.2.2 Batwara. J. M. 3.8.2.7.1 3.8.2.10.1 Baue, P. G. 3.8.3.6.2 Baumann, F.-W. 3.7.3.6 Baumard, J. F. 3.10.1.2.3 Bauschlicher, C. W. 3.8.2.1.1 Bayer, E. 3.1 1.6.1.1 Beal, k R. 3.11.6.1.3 Beaulieu, W. B. 3.8.2.6.2 Beck. W. 3.7.3.6 Becker, E.I. 3.7.2.6.3 Bednorz, J. G. 3.10.3.2.1.2 Beeby, J. L. 3.1 1.6.1.1 Behzadi, K. 3.8.2.6.3 Bein, T. 3.11.5.1
3.11.6 3.11.6.1.1 3.11.6.1.7 3.11.6.2 3.11.6.3 Beinert. H. 3.8.3.6.3 Belevskii, V. N. 3.8.2.9.1 Bell, W. 3.7.4.7 Benabbas, B. 3.10.3.3.5.2 Benazeth, S. 3.11.6.3 Bencini, A. 3.8.3.4.3 3.8.3.5.1 Beniere, F. 3.10.1.2 Benmoussa, A. 3.10.3.3.5.1 Bennett, G. M. 3.7.3.2 Bensch, W. 3.11.6 3.11.6.4.1 Bereman, R. D. 3.7.3.4.2 Berezin, B. D. 3.7.2.3.1 3.8.2.3.2 Berg, J. M. 3.8.3.6.1 Bergen, H. A. 3.7.3.3 Berger, H. 3.11.1 Bergmann, D. 3.7.3.6 Berkenblit, M. 3.10.3.4.2 Berlin, A. M. 3.8.2.10.1 Bernard, L. 3.1 1.6.1.5 3.11.6.1.6 Bernier, P. 3.11.6.1.2 Bernstein, J. L. 3.10.3.3.1 Berrie, J. D. 3.10.3.2.2.2 Berry, M. 3.10.3.4.2 Bertaut. E. F.
31 0 Bertaut, E. F. (Continued) 3.10.2.3.5 Berthet, G. 3.10.2.3.5 Besenbacher, F. 3.8.2.1.1 Besenhard, J. 0. 3.1 1.6.1.1 3.1 1.6.1.2 3.11.6.1.5 3.1 1.6.4.2 Bettman, M. 3.10.3.2.2.2 Betz, P. 3.7.3.6 Beurskiens. P. R. 3.7.3.4.1 Bevan, D. J. M. 3.10.1.5.3 3.10.1.5.5 3.10.2.2.3 3.10.3.1.3 3.10.3.4 Bevan, J. M. 3.10.3.4.1 Bever, R. S. 3.10.2.1 Bhaduri, S . 3.8.4 Bharara. P. C. 3.8.2.4.2 Bhat, A. N. 3.8.3.4.2 Bhat, I. B. 3.7.4.7 Bianchini, C . 3.8.4 Biberacher, W. 3.11.6.1.5 3.11.6.1.7 Bichon, J. 3.1 1.5.2 Bierstedt, P. E. 3.7.4.1.1 Bigham, W. S. 3.8.3.6.3 Bill, E. 3.7.3.6 Billups, W. E. 3.8.2.11.1 Biltz, W. 3.8.3.1.1 Birker, P. J. M. W. L 3.7.3.6 Bischoff, F. 3.8.2.10.1
Author Index Bishop E. 3.8.2.10.1 Bishop, P. T. 3.8.3.6.3 Bissessur, R. 3.11.6.1.7 Bither, T. A. 3.7.3.1.1 3.7.4.1.1 Blackburn. T. F. 3.8.2.1.3 Blaha, H. 3.11.6.3 Blaire, R. 3.10.2.3.1 Blake, A. J. 3.8.3.3 Blake, D.M. 3.8.2.6.2 Blanconnier, P. 3.7.4.7 Blandeau, L. 3.1 1.6.2 Bleshinskii, S. V. 3.8.2.9.1 Blitz, H. 3.7.3.2 Block, B. 3.8.4 Block, E. 3.7.3.6 Bloem, J. 3.11.3.1 Bochmann, M. 3.8.2.4.2 3.8.2.4.3 3.8.2.10.1 3.7.4.6.1.2 3.1.4.6.2.2 3.7.4.6.2.3 3.7.4.6.2.6 3.7.4.7 Bockris, J. M. 3.11.6 Bodek, I. 3.1.2.1.2 Bodroux, F. 3.7.3.2 Boersma, J. 3.7.2.4.2 3.7.2.5 Bbgge, H. 3.7.3.6 3.8.3.6.1 3.8.4 Bohmann. D.
3.7.3.2 Bohra, R. 3.8.2.7.1 3.8.2.7.2 Boilot, J. P. 3.10.3.2.2.2 Bois, C. 3.8.2.1.3 Bolinger, C. M. 3.8.4 Boller, H. 3.8.3.6.1 3.11.6 3.11.6.2 3.11.6.4.1 3.11.6.3 Bollinger, J. C. 3.7.4.6.2.1 Bollinger, J. D. 3.8.4 Bombieri, G. 3.8.2.6.1 Bonamico, M. 3.7.4.6.2.5 3.8.3.2.2 Bonasia, P. J. 3.7.4.6.2.4 3.7.4.7 Bonneau, P. 3.8.3.6.1
3.11.6.1.4 Bonziag, W. 3.7.4.5 Boorman, P. M. 3.8.3.6.3 Borel, M. M. 3.10.1.3.3 3.10.3.3 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.2 3.10.3.3.5.3 3.10.3.3.5.4 Boscola, E. J. 3.8.2.1.2 Bosnich, B. 3.7.3.6 Bossek, U. 3.8.3.6.1 Boston, C. R. 3.8.2.2.1 Boston, G. R. 3.8.2.2.1 Bottcher, P. 3.8.3.6.2 3.11.7.2
31 1
Author Index Bottomley. F. 3.8.2.1.3 3.8.4 Bouchard. R. J. 3.7.3.1.1 3.7.4.1.1 Boudjouk. P. 3.8.3.6.1 Boukamp, B. A. 3.11.6.1.2 Bourret, E. D. 3.7.4.6.2.4 Bouwmeester, H. J 3.11.6.1.2 Bowen, A. R. 3.8.2.2.1 3.8.2.7.1 Bowmaker, G. A. 3.7.3.6 Bowman, R. G. 3.8.2.1.2 Boyde. P. D. W. 3.8.3.6.1 Bracconi, P. 3.10.2.3.1 3.10.2.3.5 Brach, B. 3.10.3.1.1 Bradley, D.C. 3.8.2.4.2 3.8.2.10.1 3.8.3.4.3 Brand, H. 3.8.3.6.2 Brasted, R. C . 3.7.2.2.1 Brauer, G. 3.7.3.1.1 3.7.3.2 3.7.3.6 3.7.4.1.1 3.7.4.1.2 3.7.4.2.1 3.7.4.3 3.7.4.4 3.7.4.5 3.8.3.1.1 3.8.3.1.2 3.8.3.2.1 3.8.3.6.1 Brauer. H. E. 3.1 1.6 Braun, T. 3.11.6 3.11.6.4.1 Brebrick. R. F.
3.10.3.4 Brec. R. 3.11.6 3.1 1.6.1.1 3.11.6.2 Breckpot. R. 3.11.5.2 Brennan. J. G. 3.7.4.6.2.4 3.7.4.6.2.9 3.7.4.7 Brezeanu. M. 3.7.2.1.2 Briant. J. L. 3.10.3.2.2.2 Brilkina. T. G. 3.7.2.1.3 3.7.2.3.1 Brimor, E. 3.8.3.2.1 Brisdon. B. J. 3.8.2.6.3 Britnell, D. 3.8.4 Brodie, A. M. 3.7.3.3 3.8.2.6.1 Brohand, L. 3.10.3.3.2 Broli. M. 3.10.2.2.3 Brotherton, P. D. 3.7.3.3 Brower. W. S. 3.10.3.4.1 3.10.3.4.2 Brown, D. 3.8.2.6.1 3.8.2.6.3 3.8.2.7.1 3.8.3.4.2 Brown, D. A. 3.8.2.4.3 Brown, D. H. 3.8.2.10.1 Brown, D. S. 3.7.2.4.1 Brown, H. C. 3.8.2.7.1 Brown. H. L. 3.7.3.3 Brown, J. H. 3.7.2.1.3 Brown, T. M. 3.8.3.4.2 Browne. J. M.
3.10.3.1.3 Browning, J. 3.8.2.6.1 Bruce, D. 3.7.4.7 Bruce, J. M. 3.7.2.2.2 Bruck, R. 3.7.3.5.1 Bmkl. A. 3.7.4.3 Brunelli. M. 3.8.2.4.2 Brunie. S. 3.1 1.4.1 3.11.4.2 Brunner, H. 3.8.4 Brunori. M. 3.8.2.1.2 Brus, L. E. 3.7.4.7 Buerger. M. J. 3.10.3.3.2 Buheitl. F. 3.1 1.6.1.5 Bukhanevich, V. F. 3.11.4.1 Bukhtiyarov. V. I. 3.7.2.1.3 Bulliner. P. A. 3.9.3 Bunzli. J. C. G. 3.8.2.7.1 Burbank. R. D. 3.9.3 Burdett. J. K. 3.7.2.8 Burel, L. 3.11.7.2 Burgi. H. B. 3.7.3.2 Burgi. H. B. 3.7.3.6 Burmeister. J. L. 3.8.3.2.2 Burns, J. H. 3.8.2.7.1 Bums, R. P. 3.7.3.4.1 3.7.3.4.2 3.7.3.5.1 3.8.3.5.1 3.8.3.5.2 Burnsteiner. J. L. 3.7.4.6.2.7
312 Burrow, T. E. 3.8.3.6.3 Burschka, C. 3.7.3.6 Bursill, L. A 3.10.1.2.1 3.10.1.2.3 3.10.1.4.2 3.10.1.5.3 3.10.1.5.4 3.10.3.1.1 3.10.3.1.2 3.10.3.3.5.5 Burstall, F. H. 3.7.3.3 Bunvell, Jr., R. L. 3.8.2.1.2 Buseck, P. R. 3.10.1.4.1 3.10.1.4.2 Butler, B. D. 3.10.1.5.5 Butler, H. 3.9.2 Buttner, H. 3.8.3.4.2 Butz, T. 3.11.6 3.1 1.6.1.1 3.11.6.1.2 3.1 1.6.1.5 3.1 1.6.1.6 Bwembya, G. 3.7.4.6.2.3 3.7.4.7 Bwembya, G. C. 3.7.4.6.2.6 3.1.4.7 Byers, W. 3.8.3.4.2
C
Cabri. L. J. 3.7.4.1.2 Cai, L. 3.8.3.6.1 Cais, M. 3.11.6.1.5 3.11.6.1.6 Cajipe, V. 3.1 1.6.1.6 Calabrese, J. C. 3.1.3.2 3.7.3.6 Calage, Y. 3.11.6.2
Author Index Calderazzo, F. 3.8.2.8.2 Caldwell, W. E. 3.7.4.5 Caletka. R. 3.11.5.1 Callahan. K. P. 3.8.3.2.1 3.8.3.6.1 Callighan, H. 3.8.2.1.2 Cambi, L. 3.11.5.1 Campana, C. 3.8.4 Camus, k 3.7.2.2.2 Canadell. E. 3.10.3.3.5.1 3.11.6.3 Candlin, J. P. 3.8.2.9.1 3.8.2.9.2 Canty, A. J. 3.7.4.6.1.2 3.7.4.6.2.3 Capmany. P. Ruiz-Dana 3.7.4.1.1 Capponi, J. J. 3.10.3.2.1.2 Carbini, A. 3.8.2.2.2 Carides, J. N. 3.10.3.2.4.1 Carlin, R. L. 3.7.2.4.1 Carpy. A. 3.10.3.2.1.5 Carrefio, T. Gonzalez 3.10.2.3.1 Carroll, P. J. 3.7.4.7 3.11.6.3 Carter, S. 3.10.3.2.1.1 Carty. A. J. 3.1.4.6.2.7 Casal, B. 3.1 1.6.1.7 Casey, A. T. 3.8.2.4.1 3.8.3.4.2 Cash, A. G. 3.7.3.3 Cashman, R. J. 3.11.7.1
Castles, J. R. 3.10.2.2.1 Catlow. C. R. A. 3.10.1.2 3.10.1.2.1 3.10.1.2.3 3.10.2.2.1 3.10.2.2.3 3.10.2.3.1 3.10.2.3.3 Cava, R. J. 3.10.3.2.1.1 3.10.3.3.1 3.10.3.3.2 Cavell, R. G. 3.8.3.4.2 Cecconi, F. 3.8.3.6.1 Cefola, M. 3.8.2.7.1 Chabre, Y. 3.1 1.6.1.1 Chada, R. K. 3.7.4.6.2.4 Chagas, A. P. 3.7.2.4.1 Chaillout, C. 3.10.3.2.1.2 Chakravarti, B. N. 3.8.2.10.1 Challen, P. R. 3.8.3.6.1 Chamberlain, L. R 3.8.2.1.3 Chan, N. H. 3.10.2.3.1 Chan. S. C. 3.8.2.2.1 Chan. S.-J. 3.7.3.1.2 Chang. A. J. 3.8.3.6.2 Chapman, S. K. 3.7.3.3 Charles, R. G. 3.8.2.7.1 Charpin, P. 3.8.2.7.1 Chatterjee, A. K. 3.8.2.10.1 Chattoraj, S. 3.8.2.7.1 Chau, C.-N. 3.8.4 Cheetham, A. K. 3.10.1.2.1
313
Author Index 3.10.1.5 3.10.2.2.1 3.10.2.2.3 3.10.3.1.3 3.10.3.2 3.10.3.2.1.1 3.10.3.2.4.1 3.10.3.3 3.10.3.3.1 3.11.6.2 Chen, C. H. 3.11.6.3 Chen. C. J. 3.10.3.3.3 Chen, H. W. 3.7.3.3 3.8.3.4.2 Chen. J. 3.8.2.1.3 Chen, J. H. 3.11.7.2 Chen, S.-J. 3.8.3.6.3 Chen, Z. 3.7.3.6 Cheng, C. R. 3.8.3.6.1 Cheng, Y. F. 3.7.4.6.2.9 3.7.4.7 Cheon, J. 3.8.3.6.3 Chernick. C. L. 3.9.2 Chernyaev, I. I. 3.8.2.10.1 Chertihin, G. V. 3.8.2.1.1 Cheung, S. K. 3.8.2.1.2 Chevalier, P. 3.11.6.1.1 3.1 1.5.2 Chevrel. R. 3.11.6 3.11.6.3 3.1 1.6.4.2 3.11.7.2 Chevreton. M. 3.11.4.1 3.11.4.2 Chianelli, R. R. 3.8.3.1.1 3.8.3.6.1 3.8.3.6.2 3.11.6.3
Chiesi-Villa. A. 3.8.2.8.3 Chikashige, M. 3.7.4.1.1 3.7.4.1.2 Chin, T.-T. 3.8.4 Chisholm, M. H. 3.8.2.4.2 3.8.2.4.3 Chivers, T. 3.7.3.6 3.8.2.11.1 3.8.3.7.1 Chizhikov, D. M. 3.7.4.1.1 3.7.4.1.2 3.7.4.2.1 3.7.4.3 3.7.4.4 3.7.4.5 Cho, B. R. 3.8.2.11.1 3.8.3.7.1 Choisnet, J. 3.10.3.3 3.10.3.3.3 Chorghade, G. S. 3.8.4 Choy, A. 3.7.3.6 3.7.4.6.2.1 Choy, V. J. 3.8.2.1.2 Christe. K. 0. 3.9.2 Christian, P. A. 3.10.3.2.4.1 Christou. G. 3.7.3.6 3.8.3.2.1 3.8.3.6.1 Christuk, C . C. 3.7.4.6.2.1 Chu. M. 3.7.3.1.2 Chudnov, A. F. 3.7.2.1.2 Ciampolini. M. 3.8.2.7.1 Cini, R. 3.8.2.7.1 Ciurli, S. 3.8.3.6.3 Claassen. H. H. 3.9.2
Clark, G. R. 3.8.3.6.1 Clark. R. J. H. 3.8.2.4.1 Clarke, B. 3.8.2.6.1 Clavijo, R. 3.11.6.2 Clayden. N. J. 3.11.6.4.2 Cleary, D. A. 3.11.6.1.7 Clegg, W. 3.7.3.6 Clement, R. 3.1 1.6.2 Clement, R. P. 3.11.6.1.7 Clerc, D. G. 3.11.6.1.7 Cloud, W. H. 3.7.3.1.1 3.7.4.1.1 Coates, G. E. 3.7.2.2.2 3.7.2.4.2 Cockayne. B. 3.7.4.7 Cohen, H. 3.8.2.1.3 Cohen, J. B. 3.10.1.2.1 3.10.2.2.1 Cohen. R. L. 3.8.4 Colcolough, T. 3.7.3.4.2 Cole-Hamilton, D. J. 3.7.4.7 Coles, S. J. 3.7.4.6.2.6 Collin, G. 3.11.4.2 3.1 1.6.4.2 Collison. D. 3.8.3.6.3 Collongues. R. 3.10.3.2.2.2 Colombet, P. 3.11.5.2 3.11.6.1.5 3.11.6.1.6 Compin, L. 3.8.3.4.2 Conroy, L. E. 3.8.3.1.1
31 4 Conroy. L. E. (Continued) 3.8.3.1.2 Contreras-Ortega, C. 3.11.6.2 Conway, B. E. 3.11.6 Cooper, J. J. 3.10.1.3.3 Cooper, W. C. 3.7.4.6.2.7 Copley, D. B. 3.8.2.6.3 Cordes, A. W. 3.8.4 Cordfunke, E. H. P. 3.10.3.4.3 Corfield, P. W. R. 3.7.3.3 Corrnack, A. N. 3.10.1.2.3 Cornman, C. R. 3.8.2.1.3 Cors, J. 3.11.7.2 Costentin, G. 3.10.3.3 3.10.3.3.5 3.10.3.3.5.2 Costes, R. M. 3.8.2.7.1 Cotton, F. A. 3.7.2.1.1 3.7.2.2.2 3.7.2.4.1 3.7.3.1.1 3.7.3.2 3.7.3.6 3.7.4.6.2.7 3.8.2.1.1 3.8.2.2.1 3.8.2.2.2 3.8.2.4.2 3.8.2.4.3 3.8.2.7.2 3.8.3.1.1 3.8.3.5.1 3.8.3.6.2 Cottril. S. M. 3.7.3.2 Coucouvanis, D. 3.7.3.1.2 3.7.3.2 3.7.3.4.1 3.7.3.4.2 3.7.3.6 3.8.3.2.1
Author Index 3.8.3.2.2 3.8.3.4.1 3.8.3.4.2 3.8.3.4.3 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.11.4.2 Coughanour. L. W 3.10.3.4.1 Courtois, A. 3.10.3.3.5.2 Cowley. A. 3.8.2.6.3 Cowley, A. H. 3.8.4 Cowley, J. M. 3.10.3.1.3 Cox, D. E. 3.11.5.1 Cox. D. F. 3.7.2.1.3 Cox. D. M. 3.8.2.1.1 Cox, P. A. 3.7.2.1.1 3.8.2.1.1 3.11.6.1.7 Craig, D. C. 3.7.3.6 3.7.4.6.2.1 3.7.4.6.2.3 3.8.4 Cramer, R. E. 3.8.3.6.1 3.8.3.6.3 Cramer, S. P. 3.8.3.6.2 Cras. J. A. 3.7.3.4.1 3.7.3.5.2 3.8.3.4.1 3.8.3.4.2 Crawford. E. S. 3.10.3.1.3 Cremer-Lober, B. 3.9.2 3.9.3 Crist, D. R. 3.7.2.4.1 Cristou, G. 3.8.3.6.3 Critchlow. P. B. 3.8.3.4.2 Cronin. J. L. 3.7.3.6
3.8.3.2.1 3.8.3.6.2 Cros, C. 3.1 1.6 Crosse, B. C. 3.8.3.6.3 Cundy, C. S . 3.8.2.6.1 Cunningham, D. 3.8.2.4.3 Curie, D. B. 3.10.3.2.1.1 Curtis, C. M. 3.9.2 Curtis, M. D. 3.8.2.1.3 Curzon, A. E. 3.11.6.1.2 3.1 1.6.1.5 Cusick. J. 3.8.4 Cutsforth. B C. 3.7.2.2.2
D Daalen, J. V. 3.7.2.5 Dabbousi, B. 0. 3.7.4.6.2.4 3.7.4.7 Dabrowski. B M. 3.10.3.2 3.10.3.2.1.2 Dahl, L. F. 3.8.3.6.3 3.8.4 Dahn. J. R. 3.1 1.6.4.2 3.1 1.6.2 Dale, J. W. 3.7.4.6.1.2 3.7.4.6.2.2 3.7.4.6.2.3 Dance,I. 3.7.3.6 3.8.3.2.1 3.8.4 Dance, I. G. 3.7.3.2 3.7.3.6 3.7.4.6.2.1 3.7.4.6.2.3 3.8.3.6.3 3.8.4 Dance. N. S. 3.7.4.6.1.2
315
Author Index 3.7.4.6.2.2 Dang, H. S. 3.7.2.1.3 Dankleff, M. 3.7.2.4.1 Dann, S. E. 3.10.3.2.1.1 Danot, M. 3.11.5.2 3.11.6.1.5 3.11.6.3 Dapporto. P. 3.8.2.7.1 Darkwa, J. 3.8.3.6.2 Darling, J. H. 3.7.2.8 3.8.2.11.3 Darriet, J. 3.10.3.3.3 3.10.3.2.1.4 Darriet, M. 3.10.3.3.1 Das. I. 3.8.2.1.3 Date, S. 3.10.2.3.3 Davces, J. E. D. 3.1 1.6.4.2 Davidson, A. 3.7.3.5.2 3.7.3.5.1 Davidson, M. R. 3.8.2.2.2 Davies, k G. 3.7.2.1.3 Davies. G. 3.7.2.1.2 Davies, I. 3.7.4.6.2.2 Davies, J. E. D. 3.11.6 3.11.6.1.2 3.11.6.1.6 Davies. W. B. 3.11.6.1.7 Davila, R. M. 3.7.3.5.1 Davis. R. L. 3.7.2.1.2 Davy. E. D. 3.8.3.4.2 Day, P. 3.10.3.2 3.10.3.2.4.1 3.10.3.3
3.10.3.3.1 3.11.6.2 Day, R. W. 3.8.4 Day. V. W. 3.8.2.1.3 3.8.3.6.1 3.8.4 de Rango, C . 3.8.2.7.1 de Vos. D. 3.8.2.7.1 de Villardi, G. C. 3.8.2.7.1 Dean, P. A W. 3.7.4.6.2.3 DeBoer, D. K. G. 3.11.6 DeBrabander, H. F. 3.7.3.2 Decroux. M. 3.11.7.2 Deffieux. A. 3.1.2.2.2 deFilippo, D. 3.7.3.3 Degroot, D. C. 3.11.6.1.7 Dehnicke. K. 3.7.4.6.2.1 3.8.4 Dekock, C. W. 3.8.2.11.1 3.8.2.11.3 Dell'amico, G. 3.8.2.8.2 Delmas, C. 3.10.3.2.4.5 Delphine. M. 3.8.3.4.2 deMontauzon. D. 3.8.3.6.3 Denian. J. 3.8.2.1.3 Deniard. P. 3.11.6.1.1 dePerazzo, P. K. 3.7.3.3 Derenne. S. 3.8.2.1.3 DeRidder, R. 3.11.6.1.2 Dernier, P. F. 3.10.1.2.2 Deschanvres, A 3.10.3.3
Desgardin, G. 3.10.3.3.2 Deshpande, S. 3.10.2.3.3 DesMarteau. D. D. 3.9.3 Desreux, J. F. 3.8.2.7.1 Dessy, G. 3.7.4.6.2.5 3.8.3.2.2 Detering. B. 3.7.3.6 Deutsch. E. 3.7.3.6 3.8.3.3 Deutsch. J. L. 3.8.3.1.1 3.8.3.6.1 Dev, S. 3.7.3.6 3.7.4.6.1.2 3.8.3.6.1 3.8.3.6.2 3.8.4 Devalette, M. 3.10.3.3.3 Devantay. H. 3.11.7.2 Devillanova. F. 3.7.3.3 deVos, D. 3.7.2.5 Devynck. J. 3.11.6 Dewan, J. C. 3.8.3.6.3 Dexpert, H. 3.11.6.3 Dhingra. S. 3.8.4 3.7.3.6 Dhoi. Y. 3.8.2.4.1 Dickens, P. G. 3.10.3.2.4.1 3.10.3.2.4.2 Diedering, A. 3.1 1.6.1.2 Diel, B. N. 3.11.6.1.6 Diemann. E. 3.8.3.2.3 3.8.3.2.1 3.8.3.6.1 3.8.3.6.2
316 Diessens, F. C. M. 10.2.3.2 Dilworth. J. R. 3.8.3.2.1 3.8.3.6.3 Dines. M. B. 3.8.3.6.1 3.1 1.6.1.1 3.1 1.6.1.6 3.11.6.1.7 3.11.6.3 Dion, M. 3.10.3.2.1.5 Dirand. J. 3.8.3.2.1 DiSalvo. F. J. 3.10.3.2.4.1 3.11.5.2 3.11.6 3.11.6.1.5 3.1 1.6.1.6 3.1 1.6.3 3.1 1.6.4.2 Divigalpitiya, W. M. R. 3.11.6.1.7 Do, Y. 3.8.3.6.1 Dodonov, V. A. 3.7.2.3.1 Dolphin, D. H. 3.8.2.1.2 Dolscheid, P. 3.1 1.6.4.2 Domenges, B. 3.10.3.3.5.1 Donohue. J. 3.10.3.5 Donohue. P. C. 3.7.3.1.1 3.7.4.1.1 Dorfman, J. R. 3.8.3.6.3 Dorhout, P. K. 3.7.3.6 3.1 1.5.1 3.11.7.2 Dorschner. J. R. 3.8.2.6.3 Downes, J. M. 3.1.3.6 Downs. A. J. 3.10.2.3.4 Dows, A J. 3.8.2.11.3 Doyle, G. 3.8.2.7.1
Author Index Doyle. N. J. 3.10.2.2.1 Draganjac, M. 3.7.3.6 3.8.3.2.1 3.8.3.6.3 3.8.4 Draganjac, M. E. 3.8.3.6.2 Draganjoe, M. 3.7.3.2 Drake, J. E. 3.1.4.6.2.4 Dresdner, H. C. 3.10.3.3.2 Driessen, W. L. 3.7.2.5 3.8.2.7.1 du Preez, J. G. H. 3.8.2.6.1 3.8.2.6.3 Dubost, H. 3.7.2.8 Dugast, k 3.11.6.2 Dullenkopf, W. 3.7.4.1.1 3.7.4.1.2 Dumas, J. 3.10.3.2.4.3 Duncan, J. L. 3.7.4.6.2.7 Dunham, R. H. 3.9.2 Dunham, W. R. 3.8.3.6.1 Dunitz, J. D. 3.10.3.1.3 Dunn, B. 3.10.3.2.2.2 Dunn. J. M. 3.11.6.1.6 Dunne. M. 3.8.2.7.2 Duran, R. 3.11.6.2 Durand, P. J. 3.8.3.2.1 3.8.3.6.1 3.10.1.2.3 Durnyakova. T. B. 3.8.2.9.1 Duyckaerts, G. 3.8.2.7.1 Dwight. K. 3.7.2.1.1
3.8.2.1.1 Dye, J. L. 3.10.3.3.5.4 D'Yachenko. 0.G. 3.10.1.3.3 3.10.1.3.2 3.10.3.3.1
E
Earnshaw, A. 3.7.2.1.1 3.7.3.6 3.8.2.1.1 3.8.4 Eary, J. G. 3.7.3.3 Easey. J. F. 3.8.2.6.3 Ebel, E. W. 3.8.2.4.2 Eckert, H. 3.10.3.3.3 Eddy, L. P. 3.7.4.5 Eddy. M. M. 3.11.5.1 Edwards, J. 3.8.2.6.1 Edwards, J. 0. 3.7.2.4.1 Edwards, P. G. 3.8.2.10.1 Efner. H. F. 3.8.2.11.2 Egharevba. G. 0. 3.8.4 Ehsani. H. 3.1.4.1 Eichhorn. B. W. 3.8.4 Eichinger, G. 3.11.6.1.1 Eickman, N. C. 3.7.2.1.2 Eidaward. A. H. 3.8.2.4.1 Einstein, F. W. B. 3.7.4.6.2.2 3.11.6.2 Eisenberg. M. 3.9.3 Eisenberg. R. 3.7.2.6.3 3.7.3.5.2 3.8.2.8.1 3.8.2.8.2
Author Index 3.8.3.4.2 Ekstrom, T. 3.10.1.3.2 3.10.1.4.1 3.10.3.1.2 Elder, R. C. 3.1.3.6 3.8.3.3 Elduque, A. 3.7.3.5.1 Eller, P. G. 3.1.3.3 3.7.3.6 3.9.2 Elli, M. 3.1 1.5.1 Ellis, J. D. 3.8.2.2.2 Eltzner, W. 3.8.3.6.2 Erneleus. H. J. 3.7.4.1.1 3.1.4.6.1.2 3.7.4.6.2.2 3.7.4.6.2.3 Emerson, J. A. 3.8.2.11.1 Emerson, E. 3.8.2.6.1 Emge, T. 3.10.3.3.5.2 Ernge. T. J. 3.1.4.6.2.9 3.1.4.1 Ernpsall. H. D. 3.8.2.6.1 Enoki, T. 3.1 1.6.1.4 Eppinga, R. 3.1 1.6.1.2 Erernenko, I. L. 3.8.3.6.3 Erskine, R. W. 3.8.2.1.2 Eulenberger, G. 3.1 1.7.1 Evans, J. S. 0. 3.11.6 Evans, C. A. 3.1.4.6.2.1 Evans, R. P. 3.8.3.4.3 Evenboudjada. S. 3.11.1.2 Extine, M. W. 3.8.2.4.2
3.8.2.4.3 Eyring, L. 3.1.4.6.2.9 3.10.1.5.1 3.10.1.5.2 3.10.1.5.3 3.10.2.2.1 3.10.2.2.2 3.10.2.3.4 3.10.3.4 3.10.3.4.2 3.11.1 3.11.2.2
F
Faber, C. 3.7.4.3 Fachinetti, G. 3.8.2.8.3 Fackler, Jr.. J. P. 3.7.3.1.2 3.7.3.4.1 3.7.3.5.1 3.8.3.2.2 3.8.3.4.1 3.8.3.5.1 3.8.4 Fackler. J. P. 3.7.4.6.2.2 Fackler, R. 3.1 1.6.1.6 Faggiani. R. 3.8.4 Fairbrother, F. 3.8.2.6.3 Faktor. M. M. 3.11.3.1 Falbe. J. 3.11.6 Falk, C. D. 3.8.2.1.2 Fanning, J. C. 3.1.2.4.1 Fanwick. P. E. 3.8.2.4.2 Farago, M. E. 3.7.4.6.2.7 Fares. V. 3.8.3.2.2 Farneth, W. E. 3.1.3.6 Farrell, N. 3.8.2.1.2 Farren, D. W. 3.7.2.2.2 Farrington, G. C
317 3.10.3.2.2.2 Farrow, G. 3.8.2.4.2 Farver. 0. 3.7.2.1.2 Fawcett, T. G. 3.7.3.6 Fay, R. C. 3.8.3.4.2 Federov, V. E. 3.8.3.6.1 Fedin. V. P. 3.8.3.6.1 Fedotov, M. M. 3.10.3.3.1 Feenan, K. 3.8.2.6.3 Feltharn. R. D. 3.8.3.4.2 Fender, B. E. F. 3.10.1.2.1 Fendler, J. H. 3.11.5.1 Fenske, D. 3.7.4.6.2.1 3.1.4.6.2.4 3.8.3.6.1 3.8.3.6.2 3.8.4 3.11.6 3.1 1.6.4.1 3.11.1.2 Ferretti. A. 3.7.3.6 Ferretti, R. J. 3.10.3.2.4.3 Fetchin. J. A. 3.7.3.1.2 3.7.3.4.1 3.1.3.4.2 3.8.3.2.2 Field, B. 0. 3.7.2.6.1 3.1.2.6.2 3.8.2.1.2 Fierro, J. L. G. 3.10.2.3.3 Fietz, H. 3.1.3.6 Figurova. G. N. 3.7.2.1.2 Filson, M. H. 3.7.3.1.1 Fischer, J. E. 3.11.6.1.2 Fischer. 0.
318 Fischer, 0. (Continued) 3.11.6.4.2 Fisher, K. 3.8.3.2.1 3.8.4 Fisher, K. J. 3.7.3.6 3.7.4.6.2.1 3.7.4.6.2.3 FitzGerald, E. 3.11.6.1.7 Flahaut, J. 3.11.7 Flamini, A. 3.11.5.1 Flandrois, S. 3.11.6.1.1 3.11.6.1.2 3.1 1.6.1.3 3.11.6.1.5 Fleming, R. M. 3.10.3.2.1.1 Flippen, R. B. 3.7.4.1.1 Flogel, P. 3.11.3 Flohr, K. 3.9.4 Flomer, W. k 3.8.4 Floriani. C. 3.8.2.8.3 Flilkiger, R. 3.11.6.4.2 3.11.7.2 Fogler, B. B. 3.8.2.1.2 Folcher, G. 3.8.2.7.1 Folting, K. 3.7.3.6 3.8.2.1.3 Foner, S . 3.8.3.6.3 Fong, R. 3.11.6.2 Fong, R. M. 3.11.6.2 Font-Altaba, M. 3.8.3.4.3 Fontijn, A. 3.8.2.11.1 Ford, K. A. 3.1 1.6.1.7 Forde, C. E. 3.8.3.6.3
Author Index Formstone, C. 3.11.6.1.7 Forsellini, E. 3.8.2.6.1 Forward, J. M. 3.7.3.2 Fotiev, A. A. 3.10.3.2.4.1 3.10.3.3.4 Fouassier, C. 3.10.3.3.3 3.10.3.2.4.5 Fournes, L. 3.1 1.6.4.1 Foury. P. 3.10.3.3.5.1 Fowles, G. W. A. 3.8.2.6.3 3.8.4 Francis, R. 3.7.2.4.1 Francis, R. J. 3.11.6 Franco, M. A. Alario 3.10.3.1.1 Frankel. R. E. 3.8.3.2.1 Frankel. R. B. 3.8.3.6.3 Frankland, A. D. 3.8.2.1.3 Franklin, F. Y. 3.10.3.2.2.1 Franzen, H. F. 3.11.7.1 Fray. R. C. 3.8.2.7.1 Frechet. J. M. J. 3.11.6.3 Freeman, H. C. 3.7.3.6 Frey, M. 3.10.3.3.1 Friend, H. 3.11.6.1.1 Friend, R. H. 3.11.6.1.2 3.1 1.6.1.3 Fries, D. C. 3.7.3.4.1 3.7.3.1.2 3.8.3.2.2 Friesen, G. D. 3.8.3.6.1 Frindt, R. F. 3.11.5.2
3.11.6.1.2 3.1 1.6.1.5 3.11.6.1.7 Fritzler, B. 3.11.1 3.11.2.2 Fulcher, J. 3.8.2.11.1 Fulcher, J. G. 3.8.2.11.1 3.8.3.7.1 Funk, H. 3.8.2.4.2
G
Gaines, T. 3.8.3.6.3 Galitskii, P. A. 3.8.3.2.1 Gallagher, P. K. 3.10.2.3.1 3.10.2.3.5 Galy, J. 3.10.3.2.1.5 3.10.3.3.1 3.10.3.4.1 Gamble, F. R. 3.11.6.1.6 3.1 1.6.1.7 Ganal, P. 3.11.6.1.1 3.1 1.6.1.2 Ganble, F. R. 3.11.6.1.5 Gandhi, S. K. 3.7.4.7 Ganne, M. 3.10.3.2.1.5 Gannon, J. R. 3.10.3.1.1 Ganther. H. E. 3.7.4.6.2.7 Gard. P. 3.11.6 3.11.6.3 Gamer, C. C. 3.8.3.6.3 Garner, C. D. 3.7.3.6 3.8.3.6.3 Garner, C. David 3.8.3.2.1 Garrett, I. 3.11.3.1 Garthoff. D. 3.7.4.5
Author Index 3.7.4.6.2.1 Garton-Sprenger, M. B. 3.1.2.8 3.8.2.11.3 Ganvacki, W. 3.7.4.1.1 3.7.4.1.2 Gastinger, R. G. 3.8.2.11.2 3.8.3.7.2 Gatehouse, B. M 3.10.3.2.1.5 3.10.3.3.1 Gatsis. J. G. 3.11.4.2 Gattow, G. 3.7.3.6 Gaudemer, A. 3.8.2.1.3 Gaur, D. P. 3.8.2.4.2 3.8.2.7.1 3.8.2.7.2 3.8.2.10.1 Gautheron, B. 3.8.4 Geballe, T. H. 3.1 1.6.1.6 Gee, M. A. 3.11.6.1.5 Gehrer, H. 3.7.3.6 Geilmann, W. 3.7.4.2.1 Gellatly. B. J. 3.8.2.6.1 Gent, W. L. 3.7.3.2 Gerards, A. G. 3.11.6.1.2 Gerballe, T. H. 3.11.6.1.5 Gergely. A. 3.7.3.2 Ghaloun. 0.A. 3.11.5.2 Gheller. S. F. 3.8.3.6.3 Ghilardi, C. A. 3.8.3.6.1 Giacomelli, G . 3.7.2.4.2 Gibson, C. S. 3.7.3.2 Gibson, M. L. 3.8.2.6.1
Gilje. J. W. 3.8.3.6.1 Gill, J. B. 3.7.2.6.1 3.8.2.8.3 Gillard. R. D. 3.8.3.6.1 3.8.3.6.2 Gilles. J. C. 3.10.3.2.1.5 Gillespie, R. J. 3.8.4 3.9.2 Gillson. J. L. 3.7.4.1.1 Gillum, W. 0. 3.7.3.2 Gilman, H. 3.7.3.2 Gindelberger. D. E. 3.7.4.6.2.4 3.7.4.7 Gingerich. R. W. 3.8.3.6.1 Ginsberg, A. P. 3.7.4.6.1.2 3.8.4 Giolando, D. M. 3.8.3.6.2 3.8.3.6.1 3.8.4 Girolami, G . S. 3.8.3.6.3 Giroult, J. P. 3.10.3.3.5.1 Girshovich. A. S. 3.8.2.10.1 Gitlitz, M. 3.8.3.4.3 Gladysz, J. 3.8.2.11.1 Gladysz, J. A. 3.8.2.11.1 3.8.3.7.1 Glass, W. K. 3.8.2.4.3 Glassner, J. 3.7.4.5 Glaunsinger. W. 3.11.6.1.5 3.1 1.6.1.6 Glausinger, W. 3.11.6.1.2 Glausinger, W. S. 3.11.6.1.2 3.11.6.1.5
319 3.11.7.1 Gleitzer, C. 3.10.3.3.5.2 Gleu, K. 3.8.2.3.1 Goan, J. C. 3.8.2.7.2 Gocke, E. 3.11.6.4.2 Goggin. P. G . 3.7.3.3 Goh, L. Y. 3.8.4 Goldberg, M. 3.7.2.1.2 Golden, J. H. 3.11.6.3 Golebom, P. 3.7.4.2.1 3.7.4.3 Golgotiv. T. 3.8.2.10.1 Goller, E. J. 3.7.2.4.2 Golub. A. S. 3.1 1.6.1.5 Golubov, A. V. 3.7.4.1.1 Goncharov. A. F. 3.10.3.2.1.1 Gonzalez, G. 3.11.6.1.7 Goodall, D. C. 3.7.2.6.1 3.8.2.8.3 Goodenough, J. B. 3.10.2.3.4 3.11.6.4.2 Goodfellow R. J. 3.7.3.3 Goodgame. D. M. L. 3.1.2.4.1 3.7.4.6.2.1 Goodgame. M. 3.7.4.6.2.7 Goodman, C. H. L. 3.11.1 3.11.3 Gopalakrishnan. J. 3.7.3.6 3.10.3.2 3.10.3.2.1.1 3.10.3.2.2.1 3.10.3.2.4.6 3.10.3.3 3.10.3.3.1
320 Gorbunov, N. V. 3.7.2.3.1 Gordon, N. 3.7.4.5 Goreaud, M. 3.10.1.3.3 3.10.3.3 3.10.3.3.1 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.4 Gorochov, 0. 3.11.6.4.2 Gosta. G. 3.7.2.2.2 Goto, M. 3.10.3.1.3 Goubeau, J. 3.1.4.1.1 3.7.4.1.2 Gougeon, P. 3.11.6.3 3.1 1.6 Gould, R. 0. 3.8.3.3 Gozum, J. E. 3.8.3.6.3 Grachev, S. A. 3.9.4 Grandin, A. 3.10.1.3.3 3.10.3.3 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.2 3.10.3.3.5.3 3.10.3.3.5.4 Gray, H. B. 3.1.3.5.2 Green, M. 3.8.2.6.1 3.8.2.6.2 Green, M. L. H . 3.11.6.1.7 Green, N. D. 3.8.2.3.1 Greenblatt, M. 3.10.3.2.1.1 3.10.3.2.2.2 3.10.3.2.4.3 3.10.3.3 3.10.3.3.2 3.10.3.3.3 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.2
Author Index 3.1 1.4.2 3.11.6.4.1 Greenwood, N. N. 3.7.2.1.1 3.7.3.6 3.8.2.1.1 3.8.4 Grenier, J. C. 3.10.2.3.3 3.10.3.2.1.4 Greogire. C. R. 3.8.2.2.1 Grey, I. E. 3.10.2.2.3 3.10.3.1.1 Gries, T. 3.1.4.6.2.7 Griffith, E. H. 3.7.3.3 Griffths, R. J. M. 3.7.4.7 Grim, S. 0. 3.7.4.6.2.6 Grimes, C. J. 3.8.2.1.2 Grinter, R. 3.7.4.7 Grosse, A. V. 3.9.4 Groult, D. 3.10.3.2.1.2 3.10.3.3.5.1 Groy, T. L. 3.8.3.6.1 Gruber, J. 3.8.4 Grubessi, 0. 3.11.5.1 Gruhl, A. 3.8.2.7.2 Grundy, K. H . 3.8.2.6.3 Grundy, K. R. 3.8.4 Gschneider, K. A. 3.11.1 3.11.2.2 Gschneidner, Jr., K. S. 3.10.2.2.2 Guastini. C. 3.8.2.8.3 Guittard, M. 3.11.7 Gunn. S. R. 3.9.1 GUO.G.-H.
3.8.3.6.2 Gupta, B. D. 3.8.2.1.3 Gupta, J. 3.8.3.4.2 Gupta. T. R. 3.1.4.6.2.6 Gupta. V. D. 3.8.2.4.2 Gusev, Y. K. 3.9.4 Gut, R. 3.8.2.10.1 Guzman, R. 3.1 1.6.1.1 3.1 1.6.1.4 Gwet, S. P. 3.11.6.3 Gysling, H. J. 3.7.4.6.2
H
Ha-Eierdanz, M.-L. 3.8.4 Haange, R. J. 3.11.6 3.1 1.6.1.1 3.11.6.1.2 Haas. C. 3.11.1
3.11.2.1 Haas. T. E. 3.7.4.6.2.1 Haberkorn, R. A. 3.1.3.2 Hachgenei, J. 3.8.3.6.1 3.8.4 Hackett, P. A. 3.8.2.1.1 Hadawi, B. 3.8.3.6.3 Haddock, S. R. 3.1.3.3 Hadjikyriacou, A. I. 3.8.3.2.1 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.11.4.2 Haering, R. R. 3.11.6 3.11.6.1.1 Hagen, A. P. 3.11.6.1.1 Hagen. K. S.
Author Index 3.8.3.6.1 3.8.3.6.3 Hagenmark K. 3.10.2.2.3 Hagenmuller, P. 3.10.2.3.3 3.10.3.2.1.4 3.10.3.2.2.2 3.10.3.2.4.5 3.10.3.3 3.10.3.3.1 3.10.3.3.3 3.10.3.3.4 Hagihara, N. 3.8.2.5.1 Hahn, H. 3.11.7.1 Haiduc. I. 3.8.3.4.2 Hails, J. E. 3.7.4.7 Haire, R. G. 3.10.2.2.2 Haitko, D. A. 3.8.2.4.2 3.8.2.4.3 Halbert, T. R. 3.8.3.2.2 Hall, R. C. 3.8.3.2.1 Hall, R. D. 3.7.4.2.1 Hall, W. K. 3.11.4.2 Hamilton, W. C. 3.8.2.7.1 Han, IC R. 3.8.2.1.3 Han, Y. 3.7.3.6 Hancock. R. D. 3.7.2.2.2 Hanlan, A. H. 3.8.2.1.1 Hanlan, L. k 3.8.2.11.3 Haradem, S. 3.7.3.6 Haraldsen, H. 3.8.3.1.1 Harbrecht. B. 3.11.6.1.2 Hardcastle, K. I. 3.8.2.4.1 Hardel. K. 3.7.4.2.2
Hardy, C . J. 3.7.2.6.1 3.7.2.6.2 Hargus, B. 3.8.4 Harless, M. 3.7.3.5.1 Harlow, R. L. 3.8.2.6.2 Harman. M. 3.7.4.1 Harman, M. E. 3.8.2.7.1 Harmick, Y. M. 3.8.2.1.1 Harold, R. J. 3.7.2.2.2 Harrison, H. R. 3.10.2.2.1. Harrison, S. E. 3.10.2.1 Harrison, W. D. 3.7.2.6.1 3.8.2.8.3 Hart, D. W. 3.8.2.1.3 Hart, F. A. 3.8.2.7.1 Hart, R. L. 3.8.2.1.3 Hartman. F. k 3.8.2.7.2 Hasegawa, M. 3.8.2.11.1 3.8.3.7.1 Hashimoto, H. 3.7.2.2.2 Hashimoto, T. 3.7.2.7.1 3.7.2.7.2 Hashino, Y. 3.10.2.3.5 Haszeldine, R. N. 3.8.2.7.1 Hatfield. M. R. 3.8.2.10.1 Hatko, D. A. 3.8.2.4.2 Hattori, H. 3.7.2.8 Hauge, R. H. 3.8.2.11.1 Hauptmann. A. 3.1 1.6.1.7 Haushalter, R. 3.10.3.3.5.3
321 Haushalter, R. C. 3.8.4 3.10.3.3.5.4 Hawthorne, J. 0. 3.8.2.1.2 Hayman, P. W. 3.10.2.3.1 Haynon, E. 3.7.2.1.2 Hayward, P. J. 3.8.2.6.2 Hazeldine. R. N. 3.7.4.6.1.2 3.7.4.6.2.2 3.7.4.6.2.3 Hazeltine, M. W. 3.9.4 Healy, P. C . 3.7.3.3 Heasley, G. E. 3.9.2 Heasley, V. L. 3.9.2 Heber, R. 3.7.3.5.1 Hecht, H. 3.8.2.8.1 Hecht, C. 3.8.4 Heckley. P. R. 3.8.2.7.1 Heeg, M. J. 3.7.3.6 Hegenmuller. P. 3.10.3.2.4.1 Heijer. M. D. 3.7.2.4.1 3.7.2.5 Heinrich, D. D. 3.7.3.3 3.7.3.5.1 Heising, J. 3.1 1.6.1.7 3.11.7.2 Helgesson. C . 3.11.6.2 Helmer. M. 3.8.2.1.1 Helmer, 0. 3.1 1.6.4.1 Hemmerich. P. 3.7.3.6 Hems, P. 3.7.3.2 Hencher, J. L. 3.7.3.6
322 Hendra, P. J. 3.7.4.6.2.8 Hendrickson, A R 3.8.3.4.1 Hendriksen, D. E. 3.7.2.6.3 3.8.2.8.1 3.8.2.8.2 Henkel, G. 3.7.3.6 3.8.3.6.2 3.8.3.6.3 3.8.4 Henkel, G. J. 3.8.3.6.3 Hennig, G. H. 3.11.6 Hennings, D. 3.10.2.3.1 Henrici-Olive, G. 3.8.2.1.2 Henshaw, G. 3.7.4.1.1 3.7.4.1.2 Herber, R. 3.10.3.3.3 Herberhold. M. 3.8.3.6.2 3.8.4 Herdtweck. E. 3.8.3.6.2 3.8.4 Herein. D. 3.7.2.1.1 Hermann, A. M. 3.10.3.2.1.2 Hermann, G. 3.8.2.4.2 Hernan, L. 3.11.6.1.4 Hernnann. W. A. 3.8.4 3.8.3.6.2 Herron, N. 3.7.3.6 3.1 1.5.1 Hervieu, H. 3.10.3.2.1.2 Hervieu, M. 3.10.3.2.1.1 3.10.3.2.2.1 3.10.3.3.2 3.10.3.3.3 3.10.3.3.5.1 Hess, L. 3.8.2.10.1
Author Index Hessling, G. V. 3.8.2.7.2 Hevenh. G. F. 3.7.4.2.1 3.7.4.3 Heyding, R. D. 3.7.4.1.1 Heyman. D. 3.7.2.1.3 Hibma, T. 3.1 1.6.1.1 Hidai, M. 3.8.3.6.3 Hieber, W. 3.7.3.5.1 3.8.4 Hiebl. K. 3.11.6 3.11.6.2 Higuchi, T. 3.8.3.6.3 Hilderbrand, J. H. 3.7.3.1.1 Hill, H. A. 0. 3.8.3.4.2 Hill, L. 3.8.4 Himmelwright, R. S. 3.7.2.1.2 Hinokuma, K. 3.10.2.3.1 Hioki, T. 3.10.2.3.1 Hirotsu. K. 3.8.3.6.3 Hirpo. W. 3.7.3.6 3.11.6.1.7 Hobson, R. J. 3.8.4 Hochtlen, F. 3.7.3.2 Hodby. J. 3.11.6.1.7 Hodul, D. T. 3.11.6.1.1 Hoffman, B. M. 3.8.2.1.2 Hoffman, G. G. 3.8.3.2.1 Hoffman, K. A. 3.7.3.2 Hoffman, M. Z. 3.7.2.1.2 Hoffman. W. 3.7.3.4.2
Hogrel, J. F. 3.7.4.7 Hojo, Y. 3.7.4.6.2.7 Hoke, W. E. 3.7.4.7 Holah, D. G. 3.7.3.2 3.8.3.4.2 Holder, A. J. 3.8.3.3 Hollander, F. J. 3.7.4.6.2.4 3.7.4.7 Holleman. A. F. 3.11.6 Hollenboom, L. J. 3.11.6 Holler, R. 3.8.4 Holliday, R. L. 3.8.4 Hollingsworth, D. R. 3.9.2 Holloway. J. H. 3.9.2 Holm. R. H. 3.7.3.2 3.8.3.2.1 3.7.3.5.2 3.8.3.6.1 3.8.3.6.3 3.8.4 Holm, W. 3.10.3.3.1 Holtman, D. A. 3.11.6.3 Holtzberg. F. 3.10.3.4.2 Honassen. H. B. 3.8.3.1.1 Honda. K. 3.8.2.1.2 Hong, M.-C, 3.8.3.6.1 Honigschmid, 0. 3.7.4.1.1 3.7.4.1.2 Hope. J. M. 3.8.3.4.1 3.8.3.4.2 Hoppe, R. 3.7.3.2 Hoppenjans. D. W. 3.8.2.2.1 Hor, T. S. A.
323
Author Index 3.8.3.6.1 Homer. S. M. 3.8.2.6.3 Hornyak. G. L. 3.1 1.5.1 Horvath, B. 3.8.2.4.2 Horvath, E. G. 3.8.2.4.2 Horwood, Ellis 3.8.2.4.2 Hosch, P. 3.7.4.1.1 3.7.4.1.2 Hosoya, M. 3.10.2.3.1 Houghton. J. J. 3.8.2.11.1 Houser, E. J. 3.8.4 Howard. J. k 3.7.2.1.1 3.7.3.7 Howard, J. k K. 3.8.2.6.2 Howard, J. S. 3.1.2.8 Howard, K. E. 3.8.3.6.1 Howe. D. V. 3.7.3.5.1 Howe-Grant, M. 3.8.3.6.3 Hoyer. E. 3.7.3.5.1 Hsieh, Z. H. 3.7.2.4.1 Hsu, S. P. 3.11.6.1.5 Hu. J. 3.8.3.6.3 Huan, G. 3.11.6.4.1 Huang, S. P. 3.7.4.6.2.1 Huang, S.-P. 3.7.4.6.2.1 3.8.4 Huber, H. 3.7.2.8 3.8.2.11.3 Hubler, A. 3.1 1.6.1.5 Huether, C. H. 3.8.2.7.2 Huffman, J. C.
3.7.3.6 3.8.2.1.3 Hug, P. 3.11.6 3.1 1.6.4.1 Hughes, D. L. 3.8.3.6.3 3.8.3.6.2 Hughes, H. P. 3.11.6 Hughey, J. L. 3.7.3.6 Hull, G. W. 3.1 1.5.2 3.11.6 3.1 1.6.1.5 3.11.6.1.7 3.11.6.3 3.11.6.4.2 Hull. Jr., G. W. 3.10.3.3.2 Huml, K. 3.7.4.1.1 Hummel, H. U. 3.11.6.1.6 Hunt, G. W. 3.7.3.3 Hunt, J. B. 3.8.2.2.1 Hunter, S. H. 3.8.2.6.1 Hurd. L. C. 3.8.3.2.1 Hursthouse, M. B. 3.7.4.6.2.6 3.7.4.1 3.8.2.4.2 3.8.2.4.3 3.8.2.7.1 3.8.2.10.1 Hussain, M. S. 3.7.4.6.2.6 3.7.4.6.2.7 Huston, J. L. 3.9.2 Hutchinson, F. G. 3.7.2.2.2 Hutchinson. J. L. 3.10.3.1.3 Huttner, G. 3.8.4 Hutton, R. S. 3.10.3.3.2 Hwu, S. J. 3.10.3.3.5.4 Hyde. B. G.
3.10.1.2.1 3.10.1.2.3 3.10.1.3.1 3.10.1.3.2 3.10.1.3.3 3.10.1.4.1 3.10.1.4.2 3.10.1.5.3 3.10.1.5.4 3.10.3.1.1 3.10.3.1.2 Hyde, G. 3.10.3.4.1 Hyde. K. E. 3.8.2.2.1 Hyde, T. I. 3.8.3.3 Hyman, H. H. 3.9.2
I
Ibers, J. A. 3.1.2.1.2 3.7.3.6 3.1.4.6.2.1 3.8.2.1.2 3.8.3.6.2 3.8.3.6.3 3.8.4 3.10.3.1.3 Ido, D. J. W. 3.11.4.2 Igaki, K. 3.11.3.1 Iguchi. E. 3.10.1.2.3 Iida. S. 3.10.2.3.5 Iijima, S. 3.10.3.1.3 3.10.3.4.2 Iizuka, T. 3.8.2.1.2 Ikeda. S. 3.8.2.7.2 Ikuta. H. 3.10.2.3.1 Imoto. J. 3.8.3.6.1 Inoue, Y. 3.8.3.6.1 Interrante. L. V. 3.8.4 Ipser, H. 3.1 1.4.1 Irvine. S. J. C.
324 Irvine, S. J. C. (Continued) 3.1.4.7 Isied, S. S. 3.8.3.2.1 3.8.3.2.3 3.8.3.3 3.8.3.5.2 Iskraut, k 3.9.3 Istomin, S. A. 3.10.3.3.1 Ito, T. 3.8.2.1.2 Itoh. M. 3.10.3.2.1.1 Iwai, S . 3.10.3.3.1 Iwamoto, R. 3.1.2.5
J
Jacobson, A. J. 3.8.3.6.2 Jacob, E. 3.9.2 3.9.3 3.9.4 Jacobsen. A. 3.1 1.6.1.5 Jacobson, A. J. 3.10.3.2.1.5 3.10.3.2.4.1 3.10.3.2.4.2 3.11.5.2 3.11.6 3.1 1.6.1.1 3.11.6.1.7 3.11.6.2 3.11.6.3 Jaegermann, W. 3.11.6 Jain, N. C. 3.8.2.4.1 James, A. C. W. P. 3.11.6.4.2 James, B. R. 3.8.3.3 3.8.2.1.2 James, J. M. 3.7.4.6.2.1 James, R. 3.10.1.2.3 Jamieson. P. B. 3.10.3.3.1 Jander. G. 3.7.2.6.1
Author Index 3.8.2.8.1 3.8.2.8.3 Janietz, N. 3.8.4 Janner, A. 3.10.1.5.5 Janssen, T. 3.10.1.5.5 Jaselskis, B. 3.9.2 Jayaraman, A 3.11.2.2 Jean-Louis, A M. 3.7.4.7 Jeannin, Y. 3.8.2.1.3 Jefferson, D. k 3.10.2.3.3 Jellinek, F. 3.7.3.1.1 3.7.4.1.1 3.8.3.1.1 3.8.3.1.2 3.8.3.2.1 3.11.1 3.11.2.1 3.1 1.6.1.1 3.1 1.7.1 Jensen, F. R. 3.7.2.1.3 3.8.2.1.3 Jeter, D. 3.8.4 Jick, B. S. 3.8.4 Jimenez, R. 3.1 1.6.1.7 Jin, G.-X. 3.8.3.6.2 Jitaru. I. 3.7.2.1.2 Joensen. P. 3.11.6.1.5 Johnansson, G. 3.8.2.2.2 Johnson. D. C. 3.10.3.2.2.3 Johnson, Jr., D. W. 3.10.2.3.5 Johnson, J. W. 3.10.3.2.1.5 3.11.6.2 Johnson, N. P. 3.8.2.3.1 Johnson, M. D. 3.8.2.1.3
Johnson, W. B. 3.11.6.1.1 Johnston, D. C. 3.11.6.1.5 Jolly, W. L. 3.10.3.2.4.1 3.10.3.3.4 Jonassen, H. B. 3.1.2.4.1 3.8.3.6.1 Jones, C. A. 3.8.3.6.2 Jones, C. H. W. 3.1.4.6.1.2 3.7.4.6.2.2 3.1 1.6.2 Jones, D. J. 3.8.4 Jones, G. R. 3.9.3 Jones, K. k 3.7.4.7 Jones. M. H. 3.8.2.1.2 Jones, P. G. 3.7.4.6.2.6 3.7.4.6.2.7 3.7.4.6.2.9 Jones, P. M. 3.7.2.8 Jones, P. R. 3.7.2.4.2 Jones. R. 3.7.3.7 Jones. R. D. 3.8.2.1.2 Jordan. G. J. 3.7.2.4.1 Jorge, R. A. 3.7.2.4.1 Jorgensen, C. K. 3.10.3.5 Joshi, K. C. 3.8.2.7.1 Jostes, R. 3.8.3.6.1 Jostsons. A. 3.10.2.2.1 Joubert. J. C. 3.10.2.3.5 Joule, J. A. 3.8.3.6.3 Jui, C. C. H. 3.11.6.4.2 Junod, A 3.11.7.2
325
Author Index ~
~~
Juza, R. 3.7.4.3
K
Kafafi, Z. 3.8.2.11.1 Kabhes, G. 3.11.2.1 Kachi, S. 3.10.3.1.1 Kahaian, A. J. 3.8.4 Kahl, W. 3.8.4 Kalck, P. 3.8.3.6.3 Kaldis, E. 3.11.1 3.1 1.2.1 3.11.2.2 3.11.3 3.11.3.1 3.11.3.2 Kaldor, k 3.8.2.1.1 Kalinkin, I. P. 3.7.4.5 Kalinnikov, V. T. 3.8.3.6.3 Kamaratos, M. 3.11.6 Kamata. M. 3.8.3.6.3 Kamegashira, N. 3.10.2.3.1 Kaminskii, B. T. 3.8.3.2.1 Kampf. J. 3.7.4.6.1.2 Kanatzidis. M. 3.1 1.6.1.7 Kanatzidis. M. G. 3.7.3.6 3.7.4.6.2.1 3.8.3.2.1 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.8.4 3.11.5.2 3.1 1.6.1.1 3.11.7 3.11.7.2 Kane. L. M. 3.8.4 Kaner. R. B.
3.8.3.6.1 Kang. Z . C . 3.10.2.2.2 Kang, D. 3.8.3.6.2 3.8.4 Kannewurf. C . R. 3.11.6.1.7 3.11.7.2 Kanodia, S. 3.7.3.1.2 Kanodia. S. K. 3.7.3.6 Kanzaki, Y. 3.11.5.2 3.11.6.1.1 Kapfenberger, W. 3.7.4.1.1 3.7.4.1.2 Kapoor, R. N. 3.8.2.10.1 Kapustkin, B. K. 3.10.3.2.4.1 3.10.3.3.4 Karagiozov, L. 3.7.4.2.1 Karayannis, N. M. 3.7.2.4.1 3.8.2.6.1 Karcher. W. 3.8.2.8.1 Karkwa. J. 3.8.3.6.1 Karlin, K. D. 3.7.3.3 3.8.4 Karlin, K. K. 3.7.3.5.2 Kasai. H. 3.7.4.7 Kasai. P. H. 3.7.2.8 Kato. M. 3.7.2.4.1 Ka tty. A. 3.1 1.7.1 Katz, J. J. 3.8.2.7.1 Katz, L. 3.7.3.6 Kauffman. W. J. 3.7.2.4.2 Kaufmann, J. M. 3.11.4.1 3.11.4.2 Kawaguchi, H.
3.8.3.6.1 3.8.3.6.3 Kawaki. T. 3.7.2.2.2 Kazimierski. M. 3.10.3.2 3.10.3.2.1.2 Keane, P. M. 3.8.4 Keijzers. C . P. 3.7.3.4.1 3.8.3.4.2 3.8.3.4.1 Kelly, D. P. 3.8.3.2.1 Kelly, R. L. 3.8.2.4.2 Kelm. H. 3.8.2.2.1 Kelty, S . P. 3.8.3.1.1 Kendall, K. R. 3.10.3.2.1.3 Kendrick. M. J. 3.8.2.1.3 Kepert, D. L. 3.7.2.4.1 3.8.2.4.2 3.8.2.6.3 Kermoo. M. 3.11.6.1.7 Kern, R. 3.11.3 Kestigan. M. 3.10.2.3.3 Keuch. T. F. 3.7.4.7 Khan, M. A. 3.7.3.6 Khan, M. I. 3.10.3.3.5.4 Kharakoz, A. E. 3.8.2.9.1 Kharif, Y. L. 3.10.2.1 Kibala. P. A. 3.8.3.6.2 Kidd. M. R. 3.7.2.5 Kienitz, C. 0. 3.7.4.6.2.9 Kihlborg, L. 3.10.3.3.5.1 3.10.3.3.1 Kihlborg, L. 3.10.1.3.3
326 Kikkawa, S. 3.1 1.6.1.1 Kikuchi, T. 3.10.3.1.3 Kilborg, L. 3.10.3.3.1 Kilner, M. 3.8.2.7.2 Kim, C. G. 3.8.3.6.1 3.8.3.6.3 Kim, K-W. 3.7.4.6.2.1 3.8.3.6.2 Kim, S. 3.8.3.6.1 Kim, S. J. 3.7.2.1.2 3.8.2.1.2 Kim, K-W. 3.8.4 Kimura, N. 3.10.3.3.3 Kimura, S . 3.8.3.6.3 3.10.3.1.3 King. M. G. 3.7.4.6.2.6 King, R. B. 3.8.2.10.1 3.8.2.7.1 3.10.3.2.2.2 Kinkead, S. A. 3.9.2 Kirin, I. S. 3.9.4 Kirschenbaum, L. J. 3.7.2.7.2 Kiskis, R. C. 3.8.2.1.3 Kjekshus, A. 3.11.6.4.1 Klabunde, K. J. 3.7.2.8 3.8.3.7.1 3.8.3.7.2 3.8.2.11.2 Klamut, J. 3.10.3.2 3.10.3.2.1.2 Klamut, P. W. 3.10.3.2 3.10.3.2.1.2 U. 3.11.6.1.2 Klason, P.
Author Index 3.7.3.2 Klein-Resnick, F. 3.10.3.2.4.1 Klemna. W. 3.8.3.1.1 Klemperer, W. G. 3.8.2.1.3 3.8.3.6.1 Klepp. K. 3.8.3.6.1 3.1 1.6.4.1 Klimes, J. 3.7.2.5 Klingen, W. 3.1 1.7.1 Klingert. B. 3.8.2.1.3 Klinowski, J. 3.11.6.1.7 Kljavins, J. 3.10.3.1.2 Klotzbucher, W. 3.8.2.11.3 Knegt. A. C. 3.1.2.5 3.8.2.7.1 Kneuper, H.-J. 3.8.4 Knoch, F. 3.8.3.6.3 Knbchel. A. 3.7.2.5 Koch, C. W. 3.9.2 Koch, F. 3.10.1.2.1 Koch, S. 3.8.3.6.3 Kochi, J. K. 3.8.2.1.2 Kodoma, K. 3.11.6 3.11.6.4.1 Koellner, G. 3.8.3.6.1 Koerntgen, C. A 3.8.2.8.3 Kofstad, P. 3.10.1.1.2 Kohsaka, M. 3.8.3.6.1 Koizumi, M. 3.11.6.1.1 Koksbang, R. 3.10.3.2.2.3 3.10.3.2.4.5
Kokubo. T. 3.8.2.7.2 Kolis. J. W. 3.7.3.6 3.7.4.6.2.1 3.7.4.6.2.8 3.8.3.6.2 3.8.4 3.11.5 Kolmnikov, I S . 3.1.2.6.3 Kolodziejski. W. 3.11.6.1.7 Komatsu, T. 3.11.4.2 Komiya, S. 3.8.2.4.2 Konak, C. 3.7.4.1.1 3.7.4.1.2 Kondo, T. 3.11.6.1.4 Konuma. M. 3.11.5.2 3.11.6.1.1 Konyaeva. G. N. 3.7.4.1.1 Koo, S. M. 3.8.3.6.1 KOO.S.-M. 3.8.3.6.1 Kopf, H. 3.8.4 Kostikas, A. 3.8.3.6.1 Kostikes, A. 3.1.3.2 Kosuge, K. 3.10.2.3.1 3.10.3.1.1 Kot, M. V. 3.7.4.1.2 3.7.4.1.1 Kovacs, J. A. 3.8.3.6.1 Kovtunenko, P.V. 3.10.2.1 Koy, J. 3.11.6 3.1 1.6.4.1 Kozlowski, A. Wickenden 3.8.3.6.2 Krabbes, G. 3.11.1 3.1 1.3.2 Kracek, F. C.
327
Author Index 3.7.4.1.2 Krachler, R. 3.11.4.1 Krajewski, J. J. 3.10.3.2.1.1 3.10.3.3.1 Kramer, C. E. 3.7.2.1.2 Krasikova. R. N. 3.9.4 Krause, R. A. 3.7.3.6 3.8.3.2.1 3.8.3.6.2 Krauter. G. 3.8.4 Krautscheid, H. 3.7.4.6.2.4 Krebs, B. 3.7.3.6 3.8.3.2.1 3.8.3.6.2 3.8.3.6.3 3.8.4 Kreiner, G. 3.11.6.1.2 Krickemeyer. E. 3.7.3.6 Kroger. F. A 3.10.1.1.1 3.10.1.1.2 3.10.1.1.3 Krbger, F. A. 3.11.3.1 Kroneck, P. 3.7.3.6 Krug, v. 3.8.3.6.1 Krumeich, F. 3.10.1.3.2 Ksanda, C. J. 3.7.4.1.2 Kubas, G. J. 3.7.3.6 3.8.3.6.2 3.8.3.2.3 Kubny, A 3.11.6.1.5 Kubota, E. 3.8.3.6.1 Kubota, K. 3.8.3.6.1 Kubota, M. 3.8.2.8.3 Kuehn, C. 3.8.3.2.1
3.8.3.2.3 Kuehn, C. G. 3.8.3.3 3.8.3.5.2 3.8.3.6.3 Kukimoto, H. 3.7.4.7 Kulifay, S. M. 3.7.4.1.1 3.7.4.1.2 3.7.4.2.1 Kulpe, J. 3.8.3.6.2 Kumar, R. 3.7.4.6.1.2 Kummer, J. T. 3.10.3.2.2.2 Kumpers, M. 3.11.6.4.2 3.11.7.2 Kunnmann, W. 3.10.3.2.4.3 Kurasawa, R. 3.7.4.1.1 3.7.4.1.2 Kurzius, S. C. 3.8.2.11.1 Kustos, M. 3.8.3.6.3 Kuznetsova, N. V. 3.7.2.1.3 K v m , R. I. 3.7.2.1.3
L
Laguna, A. L. 3.8.2.6.2 Labar. C. 3.11.5.2 Labbe, P. 3.10.1.3.3 3.10.3.3 3.10.3.3.1 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.3 3.10.3.3.5.4 Labinger. J. A. 3.8.2.1.3 Lacorre, S. 3.10.3.2.2.1 Laid, R. A. 3.8.2.7.1 Laist, J. W. 3.7.2.2.1 Lalancette, R. A.
3.7.3.6 3.8.2.7.1 Lalik, E. 3.11.6.1.7 Lamerle, J. 3.10.3.2.Q.1 Lamire, M. 3.10.3.3.5.1 Lande. S. S. 3.8.2.1.2 Lane, J. D. 3.8.3.6.1 Lappert, M. F. 3.8.2.4.3 3.8.2.4.2 Lappin, A. G. 3.7.2.1.2 Lardicci, L. 3.7.2.4.2 Larson, M. L. 3.8.2.7.2 Lasof, S. 3.7.4.1.1 Latimer, W. M. 3.7.3.1.1 Latos-Grazynski, L. 3.8.2.1.3 Latyaeva. V. N. 3.8.2.10.1 Lau, C. 3.7.3.6 Lauder, A. 3.7.2.2.2 Laurent, J. P. 3.8.2.4.1 3.8.2.10.1 LaValle, D. E. 3.10.3.5 Lavela, P. 3.1 1.6.1.4 Lawrence, J. M. 3.11.1 3.1 1.2.2 Layden, G. K. 3.10.3.3.1 Le Cras, F. 3.10.3.2.2.3 Le Lay, G. 3.11.3 Le Mehaute. A. 3.11.6.2 Leal, 0. 3.8.2.1.2 Leandri, G. 3.7.2.2.2 Lebedev, S. A.
328 Lebedev, S. A (Continued) 3.7.2.1.3 Leblanc, A 3.11.6.3 Leclaire, A 3.10.1.3.3 3.10.3.3 3.10.3.3.5 3.10.3.3.5.2 3.10.3.3.5.4 Leclaire. Raveau, B. 3.10.3.3.5.3 Lee, G. S . H. 3.7.3.6 3.7.4.6.2.1 3.7.4.6.2.3 Lee, J. D. 3.7.2.1.1 3.7.2.2.2 3.7.2.4.1 3.8.2.1.1 3.10.3.2.1.1 Lee, K. 3.8.2.3.1 Lee. S. C . 3.8.3.6.1 Legrand, A P. 3.11.6.1.1 3.11.6.1.2 3.1 1.6.1.3 Lehn, J. M. 3.7.2.5 Leligny, H. 3.10.3.3.5.2 Lel'kin. K. P. 3.8.2.4.2 Lemaux, S . 3.1 1.6.1.2 Lemmon, J. P. 3.1 1.6.1.7 Lemonias, P. J. 3.7.4.7 LeNegard. N. 3.1 1.6.4.2 Lenher, V. 3.7.4.2.1 Lentz, D. 3.9.3 3.9.4 Leonelli, J. 3.8.2.4.3 Lependina, 0. L. 3.1 1.6.1.5 Lerf, A 3.1 1.5.1 3.11.6
Author Index 3.11.6.1.1 3.1 1.6.1.2 3.11.6.1.5 3.11.6.1.6 3.1 1.6.1.7 3.11.7.2 Lerf, F. 3.1 1.6.1.1 Lerner, M. M. 3.11.6.1.7 Lesch, D. A. 3.8.3.6.1 3.8.4 Lester, R. 3.8.3.6.3 Levason, W. 3.8.2.1.2 Leverez, N. 3.7.4.1.1 Levy, F. 3.11.1 3.11.6.1.1 3.1 1.6.1.2 3.11.6.1.5 3.1 1.6.1.6 Lewandowski, J. T. 3.10.3.2.1.5 Lewis, D. F. 3.8.3.4.2 Lewis, J. 3.8.2.6.1 Li. C . 3.10.3.1.1 Li, J. 3.8.3.6.1 Li. Y.-J. 3.8.3.6.1 Liang, H.-C. 3.8.3.6.1 Liang, K. S. 3.8.3.6.2 Liang, W. J. 3.11.6.1.1 Liao. H. 3.7.3.6 Liao. J.-H. 3.8.4 Libowitz. G. 3.10.2.1 Lichtmann, L. S. 3.7.4.7 Liedtke, G. 3.10.1.3.2 Lii, K. H. 3.10.3.3.5.1 Lilburn, J.
3.7.2.2.2 Lin, C . S. 3.7.3.2 Lindmark, A. F. 3.8.3.4.2 Lindqvist, 0. 3.1 1.6.2 Lippard. S. 3.8.3.6.3 Lippert. M. 3.11.6.1.6 Little, D. 3.8.2.4.2 3.8.2.4.3 Liu, C . 3.11.6.1.5 Liu, H. 3.8.3.6.1 Livage. J. 3.10.3.2.4.1 Livingstone, S. E. 3.7.3.5.1 3.7.3.5.2 3.8.3.4.2 3.8.3.5.1 3.8.3.5.2 Llanos, J. 3.11.6.2 Lobana, T. S. 3.7.4.6.2.6 Lock, C . J. L. 3.8.2.3.1 Lockemeyer, J. R. 3.8.3.6.1 Lockledge. S.P. 3.8.2.1.3 Lockyer, T. N. 3.7.3.5.1 3.8.3.5.1 Lomax, J. F. 3.11.6.1.6 Loopstra, B. 0. 3.10.3.4.3 Loose, A 3.8.3.6.1 Lorberth, J. 3.7.2.2.2 Lord, R. C . 3.7.3.2 Loriers, J. 3.11.4.2 Lough, A. J. 3.8.3.6.3 Louis, R. 3.7.2.1.2 Low, J. Y. F.
329
Author Index 3.8.2.11.2 Lu, S.-F. 3.8.3.4.2 Lu, Y.-J. 3.8.4 Lubben, T. V. 3.8.2.1.3 Ludman, C . J. 3.8.2.10.1 Ludwig, R. A 3.7.3.4.1 3.8.3.4.2 Lugli, G. 3.8.2.4.2 Lundberg. M. 3.10.1.3.2 Lynch, C. T. 3.8.2.7.1 Lynch, T. R. 3.7.4.1.1 3.1.4.1.2
M
Ma, I. 3.7.3.6 MacChesney, J. B. 3.10.3.2.1.1 Machin. D. J. 3.8.3.4.2 Maciorowski, C. A 3.7.2.4.1 Mackrodt, W. C. 3.10.2.3.1 3.10.2.3.3 MacNicol, D. D. 3.11.6 3.11.6.1.6 3.1 1.6.4.2 MacNieal, D. D. 3.11.6.1.2 Mader, W. 3.10.1.3.2 Madyczewsky. R. 3.8.2.6.3 Maeda, H. 3.10.3.2.1.2 Magersttidt, M. 3.8.4 Magill, C. P. 3.8.2.1.3 Magini, M. 3.8.2.2.2 Magneli, A 3.10.1.2.2 3.10.3.3.1 Magneli, A.
3.10.1.5.3 Maguire, M. J. 3.8.3.6.3 Mahendra, K. N. 3.8.2.4.1 Mahesh, R. 3.10.3.2.1.1 Maheu, L. J. 3.8.3.2.2 Mahler. C . H. 3.8.4 Mahy, J. 3.11.6.1.2 Maignan. A 3.10.3.2.1.1 Main, D. J. 3.8.2.1.3 Makani. T. 3.8.4 Malik, K. M. A. Abdul 3.8.2.4.2 3.8.2.7.1 3.8.2.10.1 Malik, K. M. Abdel 3.4.7.4.7 Malik, K. M. Abdul 3.8.2.4.3 Malik, M. A 3.7.4.7 Malm, J. G. 3.9.2 Malone, S. F. 3.7.4.6.2.7 Manasevit, H. M. 3.7.4.7 Manca, P. 3.7.4.1.1 3.7.4.1.2 Mandelcorn, L. 3.10.1.3.1 3.10.1.3.2 Mandimutsira, B. S. 3.8.3.6.3 Mangani, S. 3.8.2.7.1 Mani, F. 3.8.3.4.3 3.8.3.5.1 Mann, A. W. 3.10.1.5.5 Manriquez, V. 3.11.6.1.7 Mansot, J. L. 3.1 1.6.1.4 Maple, M. P. 3.11.6.4.2
Marbach. G. 3.7.3.6 March, P. 3.10.2.3.3 Marchand, R. 3.10.3.3.2 Marcogrigano. G. 3.8.3.4.2 Marezio, M. 3.10.1.2.2 3.10.3.2.1.2 Margrave, J. L. 3.8.2.11.1 Marinder, B.-0. 3.10.1.3.2 3.10.1.3.3 Marinkovic. V. 3.11.6 Marko, L. 3.8.3.6.1 Markovskii, L. Ya. 3.7.4.4 3.7.4.5 Marks, T. J. 3.7.2.1.2 3.7.3.6 3.11.5.2 3.11.6.1.1 3.1 1.6.1.6 Marmolejo, G. 3.8.3.6.1 3.8.3.6.2 Maromo, F. 3.10.3.3.1 Marsh, P. 3.11.6.4.2 Marsicano, F. 3.7.2.2.2 Marsich, N. 3.7.2.2.2 Martell. A E. 3.7.2.7.1 3.8.2.1.2 3.8.2.1.3 3.8.2.9.1 Martin, C. 3.10.3.2.1.1 Martin, M. J. 3.8.3.6.1 Martin, R. L. 3.7.3.5.1 3.8.2.10.1 3.8.3.4.1 3.8.3.4.2 3.8.3.5.1 Marzilli, L. G.
330 Marzilli. L. G. (Continued) 3.8.2.1.3 Mascetti, J. 3.8.2.11.3 Massazza, F. J. 3.7.4.1.1 3.7.4.1.2 Masters, A. F. 3.7.3.5.1 3.8.3.4.2 3.8.3.5.1 Matasubayashi, G. 3.7.4.6.2.9 Matejka. G. 3.10.3.2.4.5 Mathey, Y. 3.1 1.6.3 Mathieu, F. 3.8.2.7.1 Matsuda. Y. 3.10.3.2.4.3 Matsumoto, K. 3.8.4 Matsumoto, 0. 3.11.6.I. 1 3.11.5.2 Matsuzaka, H. 3.8.3.6.3 Mattheiss, L. F. 3.10.3.2.1.1 Mattson, B. M. 3.8.3.4.1 Matusz, M. 3.8.3.6.2 Maue, P. G. 3.8.4 Maufras, J. L. 3.11.7.2 Maxson, R. N. 3.7.3.1.1 Maynard, J. L. 3.7.2.2.1 Mayweg, V. 3.8.3.5.1 Mazdiyasni, K. S. 3.8.2.7.1 Mazid, M. A. 3.7.3.7 3.7.4.6 Mazzei, A. 3.8.2.4.2 McAuliffe, C. A. 3.7.3.2 3.7.3.4.1 3.7.3.4.2 3.7.3.5.1
Author Index 3.7.3.5.2 3.8.2.1.2 3.8.3.4.1 3.8.3.4.2 3.8.3.4.3 3.8.3.5.1 3.8.3.5.2 McCaldin, J. 0. 3.7.4.7 McCall, J. M. 3.8.3.6.1 3.8.3.6.2 McCandlish, L. E. 3.11.6.3 McCarthy, T. J. 3.8.3.6.1 3.8.4 McCleverty, J. A. 3.7.3.5.1 3.7.3.5.2 3.7.3.6 3.8.3.5.1 3.8.3.5.2 3.8.3.6.1 3.8.3.6.2 McConnachie, J. M. 3.8.4 McCullough, F. P. 3.7.3.4.1 3.7.3.4.2 3.8.2.1.2 3.8.3.4.1 3.8.3.4.2 3.8.3.4.3 McDaniel, D. H. 3.7.2.2.2 McDonald, G. W. 3.8.2.8.3 McDonald, J. W. 3.8.3.6.1 McIntosh, D. 3.7.2.8 3.8.2.11.3 McKelvy, M. 3.1 1.6.1.2 3.11.6.1.5 3.11.6.1.6 McKelvy. M. J. 3.11.6.1.2 3.11.7.1 McKinnon, W. R. 3.11.6 3.11.6.4.2 McLendon, G. 3.8.2.1.2 McManus. N. T.
3.7.4.6.2.4 McQuillan. G. P. 3.7.4.6.2.6 3.7.4.6.2.7 McWhan, D. B. 3.10.1.2.2 McWhinnie, W. R. 3.7.4.6.2.2 Mealli, C. 3.7.2.1.2 3.8.3.2.1 3.8.4 Meerchaut, A. 3.11.1 3.11.4.2 3.11.6.1.4 3.11.6.3 Mehrotra, A. 3.8.2.10.1 Mehrotra. R. C. 3.8.2.4.1 3.8.2.4.2 3.8.2.4.3 3.8.2.7.1 3.8.2.1.2 3.8.2.10.1 Mehta. M. L. 3.8.2.10.1 Meier. W. 3.8.4 Meli, A 3.8.4 Mellnor, J. W. 3.7.2.2.1 Mellor. J. W. 3.7.3.1.1 Melsum, B. G. A. 3.7.2.4.1 Mendelcorn, L. 3.10.3.2.1.3 3.10.3.3.1 3.10.3.3.2 3.10.3.3.3 Mercer, G. D. 3.8.2.6.2 Merola, J. S. 3.8.4 Merritt. R. R. 3.10.1.5.4 Merzweiler. K. 3.8.3.6.1 3.8.4 Messina, R. 3.11.6 Metois, J. J. 3.11.3
331
Author Index Metselaar, R. 3.11.2.2 Meunier, P. 3.8.4 Mews, R. 3.9.3 Meyer, G. 3.11.7 Meyer, H. 3.11.6.1.5 Meyer, L. 3.10.3.3.5.4 Meyerstein, D. 3.8.2.1.3 Michel, C. 3.10.3.2.1.2 Mickel, J. P. 3.8.3.2.1 Midolline, S. 3.8.3.2.1 Midollini. S. 3.8.3.6.1 Miguel, D. 3.8.3.4.3 Miguel, J. A. 3.8.3.4.3 Mikkelsen, C . 3.10.3.3.3 Mikulski, C. M. 3.7.2.4.1 3.8.2.6.1 Mile, B. 3.7.2.1.1 3.7.2.8 Milius, W. 3.8.3.6.2 Miller, G. 3.7.4.7 Miller, J. T. 3.8.2.11.1 Miller, S. M. 3.7.3.6 Minkwitz. R. 3.9.2 Minten, K. 3.8.2.1.2 Mironov. Y. U. 3.8.4 Mironov, Y. V. 3.8.3.6.1 Mishchenko, A. V. 3.8.3.6.1 Mislankar, k 3.7.4.6.2.4 Misra. S. N. 3.8.2.10.1
Misra, T. N. 3.8.2.10.1 Mitchell, G. P. 3.7.4.6.2.4 3.7.4.7 Mitchell, J. C. 3.8.3.6.1 Mitchell. K. M. 3.9.3 Mitchell. N. 3.8.3.2.1 Mitchell, S. k 3.8.2.1.1 Mitsuhashi, H. 3.7.4.7 Mitsuishi, I. 3.7.4.7 Miura. K. 3.10.2.3.1 Mizetskaya, I. B. 3.7.4.1.1 Mizobe, Y. 3.8.3.6.3 Moelo, Y. 3.11.6.1.4 Mohan, N. 3.8.3.6.2 Mdhwald, H. 3.1 1.6.1.5 Mok. K. F. 3.8.3.6.1 Moiler, K. 3.1 1.5.1 Molsbeck, W. 3.9.2 Monforte, F. R. 3.10.2.3.1 Monier, J. C. 3.10.3.3.1 Montavon, F. 3.7.2.5 Montevalli, M. 3.7.4.7 Montignie, E. 3.7.4.2.1 3.7.4.4 Montoliu. F. M. Climent 3.7.4.1.1 Moody, B. 3.7.2.1.1 3.8.2.1.1 Moody, D. C. 3.8.2.7.1 Moore, F. W. 3.8.2.7.2 Moore, W. J.
3.10.2.1 Moorhouse. S. 3.8.2.7.1 Morales. J. 3.11.6.1.1 3.11.6.1.4 Morales, M. P. 3.10.2.3.1 Moreau, P. 3.11.6.1.2 Morgan, G. T. 3.7.3.3 3.8.2.7.1 Mori, K. 3.7.4.1.1 3.7.4.1.2 Morikawa, H. 3.10.3.3.1 Morimoto, N. 3.10.3.4 Morosin, B. 3.10.3.3.3 Morozova, A. S. 3.8.2.10.1 Morns, M. L. 3.8.2.7.1 Morris, R. H. 3.8.3.6.3 Morrison, S. R. 3.1 1.6.1.5 3.1 1.6.1.7 Morss, L. R. 3.11.7 Moseler, R. 3.8.2.4.2 Moser, H. C. 3.9.4 Moser, L. 3.7.4.1.1 3.7.4.2.1 3.7.4.3 Moshier, R. W. 3.8.2.7.1 Moskovits. M. 3.7.2.8 3.8.2.11.3 Moss, K. C . 3.8.2.10.1 Moss. G. P. 3.8.2.7.1 Motz. D. 3.7.4.2.2 Mrozowski, L. 3.7.2.7.2 Mueller-Westerhoff. U. T.
332 Mueller-Westerhoff, U. T. (Continued) 3.8.3.5.1 3.8.3.5.2 Muetterties, E. L. 3.8.3.4.2 Muetterties. M. C. 3.8.3.6.3 Muhler. M. 3.7.2.1.1 3.11.6.4.1 Muir, J. A. 3.11.7.1 Mujica, C. 3.11.6.2 Mukherjee, R. N . 3.8.3.4.2 Muller, A. 3.8.3.6.2 3.8.4 Miiller, A. 3.7.3.6 3.8.3.2.1 3.8.3.2.3 3.8.3.3 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.8.4 Miiller. C . 3.8.3.6.2 Miiller. K. A. 3.10.3.2.1.2 Muller. J. 3.1 1.6.4.2 Miiller, J. 3.11.7.2 Miiller, U. 3.8.3.6.1 Miiller-Warmuth, W. 3.1 1.6.4.2 Mullin, J. B. 3.7.4.7 Multani, R. K. 3.8.2.4.2 Mumme, W. G. 3.10.3.3.2 3.10.3.3.3 Miinchow, V. 3.8.3.6.3 Miinck. E. 3.8.3.6.3 Munson, R. A. 3.7.3.1.1 Murdock, T. 0. 3.7.2.8
Author Index 3.8.2.1 1.1 Murillo, C. A. 3.8.2.4.2 Murin, A. N. 3.9.4 Murphy, C. J. 3.8.3.6.2 Murphy, C. N. 3.7.3.2 3.7.3.6 Murphy, C. N. 3.8.3.2.1 3.8.3.4.2 3.8.3.6.3 Murphy, D. W. 3.8.4 3.10.3.2.4.1 3.10.3.3.2 3.11.5.2 3.11.6 3.1 1.6.1.1 3.11.6.1.5 3.11.6.1.7 3.11.6.3 3.11.6.4.2 Murphy, G. B. 3.8.3.4.2 Murray, A. D. 3.10.2.2.3 Murray, H. H. 3.8.3.1.1 Murray, 111. H. H. 3.8.3.2.2 Murray, S. G. 3.7.3.2 3.7.3.5.2 3.8.3.5.2 Musgrave, W. K. R. 3.8.2.7.1
N
Nadasdi. T. T. 3.8.3.6.3 Nagamori, M. 3.11.4.1 Nagy. A 3.7.2.1.1 Nakamura, A. 3.7.4.6.2.4 3.8.3.6.1 3.8.3.6.3 Nakumura, 0. 3.1 1.6.1.4 Nanjundaswamy, K. S. 3.7.3.6 Nanot, M.
3.10.2.3.1.5 Nardi, N. 3.8.2.7.1 Nasreldin, M. 3.8.3.6.1 Nassau, K. 3.11.3 Naumann, D. 3.9.3 Naumann. H. 3.8.2.4.2 Naumann. K. 3.9.2 Navas, C. 3.10.3.2.1.3 Nazar, L. F. 3.11.6.1.7 Nazarova, L. A. 3.8.2.10.1 Nazat, L. F. 3.1 1.5.2 Nefedov, V. D. 3.9.4 Nesbit. M. C. 3.10.3.2.1.5 3.10.3.3.1 Neskov, J. K. 3.8.2.1.1 Nesmeyanov, k N. 3.8.2.10.1
Netti, R. 3.8.2.8.2 Neuenschwander, K. 3.8.3.7.2 Newell, L. 3.7.3.1.1 Newing, C. W. 3.8.2.4.2 Newman, A. A. 3.8.3.2.2 Newton, W. E. 3.8.3.6.1 Ng, F. T. 3.8.3.3 Ng, Y. S. 3.8.2.6.1 Nguyen, N . 3.10.3.3 Nicholls. D. 3.7.2.2.2 3.8.2.2.1 3.8.2.2.2 Nicholson, T. 3.7.3.6 Nickless, G. 3.8.3.1.1
Author Index 3.8.3.1.2 3.8.3.2.1 Nieder-Vaharenholz, H. G. 3.10.3.5 Niehues, K. J. 3.10.3.5 Nielsen, J. B. 3.9.2 Nishihara, H. 3.11.6 3.11.6.4.1 Nishio, M. 3.8.3.6.3 Nobile, C. F. 3.8.2.1.3 Noda, S. 3.10.2.3.1 Nogina, 0. V. 3.8.2.10.1 NolBng, B. I. 3.11.3.2 Nolte, W. 0. 3.8.3.2.1 Noltes, J. G. 3.7.2.4.2 3.7.2.5 Nomura, R. 3.7.4.1 Norbury, A. H. 3.8.3.2.2 Noren, B. 3.8.2.2.2 Nosco, D. L. 3.8.3.3 Nostrand. Van 3.7.4.6.2.7 Nothe, D. 3.9.3 Novikov, Y. N. 3.11.6.1.5 Novotortsev, V. M. 3.8.3.6.3 Nowotny, H. 3.7.4.1.1 3.7.4.1.2 Nuber, B. 3.8.3.6.1 3.8.4 Nucciarone, D. 3.7.4.7 Nugent, W. k 3.8.2.6.2 Nygren, M. 3.10.3.3.1 Nyholm, R. S. 3.8.2.6.1
Nyman, C. J. 3.8.2.6.2
0
Oanh, H. T. T. 3.8.2.7.1 Obolonchik, V. A. 3.11.4.1 3.11.4.2 O’Brien, P. 3.7.4.1 OBryan, H. M. 3.10.2.3.1 OConnor, C. J. 3.8.2.1.2 ODaniel, H. 3.1 1.6.3 Oehler, J. 3.7.2.5 Ogden, J. S. 3.1.2.8 3.8.2.11.3 3.9.2 O‘Hare, D. 3.7.4.7 3.11.6 3.11.6.1.7 Ohmer, J. 3.8.3.6.1 3.8.4 Ohta, M. 3.11.4.2 Ohtani. T. 3.11.6 3.1 1.6.4.1 O’Keefe, M. 3.10.1.3.1 3.10.1.5.1 3.10.1.5.2 O’Keeffe, M. 3.10.1.2.3 3.10.1.3.2 3.10.1.3.3 3.10.1.4.2 3.10.2.2.1 3.10.3.1.1 3.10.3.1.2 3.10.3.4 3.10.3.4.1 3.10.3.4.2 Olazcuaga, R. 3.10.3.3.3 Olberding. W. 3.11.6.1.1 3.1 1.6.1.2 Olive, S.
333 3.8.2.1.2 Oliver, J. P. 3.7.4.6.1.2 Okada, K. 3.10.3.3.1 Okamura, T. 3.8.3.6.3 Omloo, W. P.F. k M. 3.11.6.1.1 3.11.7.1 O’Neal, S. C. 3.8.4 Ong, E. W. 3.11.6.1.2 3.11.7.1 Onoda, M. 3.10.3.2.4.3 3.11.4.2 Onoue, S. 3.11.6 3.1 1.6.4.1 Ooi. S. 3.8.4 Opferkuch, R. 3.9.2 Opperman, H. 3.11.1 3.1 1.3.2 Orioli, P. 3.8.2.7.1 Orlandini, A. 3.8.3.6.1 Osaka, K. 3.8.3.6.1
Osborn, R. B. L. 3.8.2.6.1 Osborne, D. W. 3.9.2 Osborne, J. H. 3.8.4 Osiecki, J. H. 3.11.6.1.5 3.11.6.1.6 Osterloh, F. 3.8.3.6.3 Otsuka, S. 3.8.3.6.3 Ott, H. R. 3.1 1.2.2 Ottersen, T. 3.7.3.3 Otto. L. P. 3.7.2.5 3.8.2.7.1 Ouvrard, G. 3.11.6
334 Ouvrard, G. (Continued) 3.1 1.6.1.1 3.11.6.1.2 3.11.6.2 3.11.7.1 Owen, D. G. 3.11.5.1 Ozin, G. A. 3.7.2.8 3.8.2.1.1 3.8.2.11.3 ODell, B. D. 3.8.3.6.3
P
Paez, J. 3.11.6.2 Palmer, D. k 3.8.2.2.1 Pan, W. H. 3.8.3.4.2 Pan, W.-H. 3.8.4 Pande, K. C. 3.8.2.7.1 Panis, D. 3.10.1.2.3 Pannetier, J. 3.11.6.1.1 Panson. A. J. 3.7.4.1.3 Paoli, k 3.11.7.2 Papaefthymiou, G. C. 3.8.3.6.1 3.8.3.6.3 Papageorgopoulos, C. A. 3.1 1.6 Papavassiliou, M. 3.8.4 Parant, J. P. 3.10.3.3.3 Paris, M. R. 3.8.2.1.2 Parish, R. V. 3.7.3.2 3.7.3.5.2 Park, Y. 3.7.3.6 3.8.3.6.1 3.8.4 Parker, H. S . 3.10.3.4 3.10.3.4.1 3.10.3.4.2 Parkin, I. P.
Author Index 3.7.4.1.2 Parkin. S. S . P. 3.11.6.1.3 Parkinson, B. A. 3.11.6 Parkman, E. C. 3.7.4.2.1 Parks, R. D. 3.11.1 3.1 1.2.2 Parmentier, P. M. 3.10.3.3.5.2 Parsons, J. D. 3.7.4.7 Pascher, G. 3.7.4.3 Pashinkin, A. 3.7.4.1.1 Pasquali, M. 3.8.2.8.2 Pasternak. M. 3.9.4 Pasynskii, A. A. 3.8.3.6.3 Patai, S . 3.7.4.6.2 Pataki, D. A. 3.8.4 Pathak, V. N. 3.8.2.7.1 Patil, P. R. 3.7.3.6 3.8.3.2.1 Pattanayak J. 3.11.6.1.4 Payer, k 3.11.6 3.1 1.6.4.2 Payne. N. C. 3.7.4.6.2.3 3.8.4 Pearson, R. G. 3.8.2.2.1 3.8.2.9.1 Pebler, J. 3.8.4 Pechharroman, C. 3.10.2.3.1 Pecht, I. 3.7.2.1.2 Peck, Jr., W. F. 3.10.3.2.1.1 Pedelty, R. 3.7.3.1.2 Pedersen, C. J. 3.7.2.5
Pell, M. k 3.8.4 Pellacni, G. C. 3.8.3.4.2 Pellini, G. 3.7.4.1.1 Penk. M. 3.7.3.6 3.8.4 Penneman, R. E. 3.8.2.7.1 Pennington, W. T 3.7.3.6 3.7.4.6.2.8 3.8.4 Perego, G. 3.8.2.4.2 Perkin, I. P. 3.7.4.1.1 Perrin, D. D. 3.7.2.2.2 Perrotto, A. 3.8.2.7.1 Persson, I. 3.7.2.4.1 Perutz, R. N. 3.8.2.11.3 Peteler, W. 3.11.1 Peters, C. R. 3.10.3.2.2.2 Peters. K. 3.11.6.2 Petit, B. 3.11.4.1 3.11.4.2 Petracovschi, V. 3.8.2.10.1 Petrouleas, V. 3.7.3.2 Pettel, B. 3.8.2.4.1 Pettenkofer, C. 3.11.6 Pfister. P.-M. 3.8.3.6.3 Philp, D. K. 3.10.1.5.3 3.10.1.5.4 Pickardt, J. 3.8.4 Pickett, C. J. 3.8.3.6.2 Pietronero, L. 3.11.6.1.2 3.11.6.4.1
335
Author Index Pignolet, L. H. 3.8.3.2.2 3.8.3.4.1 Pingarron, J. 3.11.6 Pisharody, R. 3.11.6.1.5 3.1 1.6.1.6 Pitzer, E. 3.7.4.5 Placa, S. J. L. 3.8.2.7.1 Plane, J. M. C. 3.8.2.1.1 Plonka, J. H. 3.8.3.7.1 Plorin, D. 3.1 1.7.2 Plurien, P. 3.8.2.7.1 Plurien. P. L. 3.9.2 Plygunov, A. S. 3.8.3.2.1 Podall, H. E. 3.8.2.7.2 Pohl, S. 3.8.3.6.3 Poiblanc, R. 3.8.3.6.3 Poliakoff, M. 3.1.2.8 3.8.2.11.3 Pollock. R. 3.8.2.1.2 Popolitov, V. I. 3.11.5.1 Popper, P. 3.10.3.2.1.1 Porowski, S. 3.11.3.1 Portemer. F. 3.10.1.3.3 Porter, L. C. 3.7.4.6.2.2 Posner, G. H. 3.7.3.6 Potdar, H. 3.10.2.3.3 Potel, M. 3.11.6 3.11.6.3 Potenza, J. A. 3.1.3.6 Potter, J. F. 3.10.3.2.1.1
Pouchard, M. 3.10.2.3.3 3.10.3.2.1.4 Pouget. J. P. 3.10.3.3.5.1 Poveda. A. 3.8.3.4.2 Powell, A K. 3.1.4.1 Power, P. P. 3.8.2.4.2 3.8.3.2.1 3.8.3.6.3 Prakash, H. 3.7.3.6 3.10.3.2.2.3 Prandtl. N. 3.8.2.10.1 Preit, C. 3.8.3.4.2 Preti, C. 3.7.3.3 Prewitt, C. T. 3.7.4.1.1 Price, S. J. 3.11.6 Prigent, J. 3.11.6 3.1 1.6.4.2 Prilipko, Y. S. 3.10.2.3.1 Prince, E. 3.10.3.4.2 Prior. A. C. 3.11.3.1 Prisedskii. V. V. 3.10.2.3.1 Prodan, A. 3.11.6 Prokofleva. G. N. 3.8.3.2.1 Pron, G. F. 3.1.4.5 Prosvirin, I. P. 3.7.2.1.3 Protas, J. 3.10.3.3.5.2 Protzenko, G. A. 3.11.6.1.5 Puddephatt. R. J. 3.7.3.2 3.7.3.3 3.7.3.5.2 Purmal, A. P. 3.7.2.3.1 Py, M. A.
3.11.6 3.1 1.6.1.1 Pye, M. F. 3.10.3.2.4.1 3.10.3.2.4.2 Pyke. D. 3.10.3.1.1 Pytlewski, L. L. 3.7.2.4.1 3.8.2.6.1
Q
Qiang. G.-H. 3.8.3.6.1 Que, Jr., L. 3.7.3.2 Queiros, M. A. M. 3.8.2.1.2 Queyroux, F. 3.10.3.2.1.5
R
Rabagliati. F. M. 3.1.2.2.2 Rabenau, A. 3.10.2.3.5 Rabenau, A. 3.1.4.1.1 3.7.4.2.2 3.1.4.3 Rabenstein, D. L. 3.1.4.6.2.7 Rabiller, P. 3.11.7.2 Rabillerbaudry, M. 3.11.7.2 Radzikovskaya, S. V. 3.11.4.1 Rae. A. D. 3.10.1.5.5 Ragains, M. L. 3.9.2 Rahlfs, P. 3.7.4.1.1 3.7.4.1.2 Raithby. P. R. 3.8.2.1.1 Rakitin, Yu. V. 3.8.3.6.3 Raleigh, C. J. 3.8.2.1.3 Ralston. D. 3.7.2.8 Ramachandran, R. 3.8.3.6.3 Ramanujachary. K. V
336 Ramanujachary, K. V (Continued) 3.10.3.2.1.1 3.10.3.3.5.2 3.11.4.2 Ramirez de Arellano, M.-C. 3.8.2.1.3 Ramli, E. 3.7.3.6 3.1.4.6.1.2 Ramos, C. 3.1 1.6.1.2 3.11.6.1.5 3.11.6.1.7 Rankin, D. W. 3.8.3.6.1 Rao, C. N. R. 3.7.3.6 3.10.1.5 3.10.1S.2 3.10.1.5.4 3.10.3.2 3.10.3.2.1.1 3.10.3.2.1.2 3.10.3.2.1.4 3.10.3.2.2.1 3.10.3.3 3.10.3.3.1 3.10.3.3.5 Rao, Ch. P. 3.8.3.6.3 Rao, G. V. Subba 3.11.6.1.2 3.11.6.1.3 3.1 1.6.1.5 3.11.6.1.6 3.11.6.1.7 Rao, K. J. 3.10.3.2 3.10.3.3 3.10.3.3.1 Rao, R. 3.8.3.4.2 Rao, S. R. 3.7.3.2 3.7.3.4.1 Rao, V. V. Krishna 3.8.3.4.2 Rappoport, Z . 3.1.4.6.2 Rasont, C. L. 3.8.3.4.2 Raston, C. L. 3.7.3.3 Ratke, B.
Author Index 3.7.4.5 Rau, H. 3.7.4.1.1 3.7.4.2.2 Rauchfuss. T. B. 3.7.3.6 3.7.4.6.1.2 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.8.4 Raveau, B. 3.10.1.3.3 3.10.1.5 3.10.1.5.4 3.10.3.2 3.10.3.2.1.1 3.10.3.2.1.2 3.10.3.2.1.4 3.10.3.2.1.5 3.10.3.2.2.1 3.10.3.2.3 3.10.3.2.4.4 3.10.3.2.4.6 3.10.3.3 3.10.3.3.1 3.10.3.3.2 3.10.3.3.3 3.10.3.3.5 3.10.3.3.5.1 3.10.3.3.5.2 3.10.3.3.5.4 3.10.3.3.5.5 Raymond, C. C. 3.7.3.6 3.11.5.1 Razi, M. T. 3.7.3.6 Razuvaev, G. A. 3.1.2.1.2 3.7.2.1.3 3.7.2.3.1 3.8.2.10.1 Reau, J. M. 3.10.3.2.4.5 Redeout. D. C. 3.8.2.4.2 Reed, C. A. 3.8.2.1.2 Reed, D. R. 3.7.2.2.2 Reed, T. B. 3.10.1.5.1 3.10.1.5.2 3.10.2.2.1 Reedijk, J.
3.7.3.6 Regitz, M. 3.11.6 Rehder, D. 3.8.4 Rehn, K. 3.8.2.3.1 Rehren, C. 3.7.2.1.1 Reichelt, W. 3.11.1 3.11.3.2 Reichert, W. 3.8.2.4.2 Reid, k F. 3.10.3.1.1 3.10.3.3.3 Reid, k H. 3.8.3.7.1 Reid, E. E. 3.7.3.6 Reid, R. 3.10.3.1.1 Reifschneider, W. 3.7.3.6 Reihlen. H. 3.8.2.7.2 Reimika. J. P. 3.10.1.2.2 Reiner, D. 3.8.4 Reingold, k L. 3.8.3.6.2 Reinhold, R. 3.10.3.2.4.1 Reisman. A. 3.10.3.4.2 Reller, A. 3.10.2.3.3 Remmert, P. 3.1 1.6.1.6 Remskar. M. 3.11.6 Renard. J. P. 3.11.6.2 Reuter, B. 3.7.4.2.2 Revelli, J. F. 3.8.3.1.1 Reynders, P. 3.7.4.1 Reynolds, J. G. 3.8.3.6.3 Reynolds, W. L. 3.7.2.4.1 3.8.2.6.1
Author Index Reznik, H. G. 3.1 1.6.1.5 3.11.6.1.7 Rheingold. A. L. 3.8.2.1.3 3.8.3.6.2 3.8.3.6.1 3.8.4 Ricard, L. 3.8.3.2.1 Rice, C. E. 3.8.4 Rice, D. A. 3.7.4.2.2 3.8.4 Rich, S . M. 3.11.6.3 Richards. R. L. 3.8.3.6.3 Richardson. D. A. 3.8.3.6.1 Richardson, M. W. 3.11.3.2 Richardson, R. E. 3.9.2 Richmann. P. N. 3.8.3.6.1 Rickard, C. E. F. 3.8.3.4.2 Ridge, B. 3.8.3.6.3 3.8.3.2.1 Ridley, D. 3.7.2.2.2 3.7.2.4.2 Rieck G. D. 10.2.3.2 Riekel. C. 3.11.6.1.7 3.11.6.1.5 Riera, V. 3.8.2.1.3 3.8.3.4.3 Riess, J. G. 3.8.2.6.3 Rietveld, H. M. 3.11.4.2 Ringaby. 0. 3.10.1.3.3 Ringy. P. 3.8.2.7.1 Riseborough. P. S. 3.11.1 3.11.2.2 Ritsma, J. 3.11.6.2
Ritter, C. 3.11.6.1.5 Robers, M. W. 3.10.1.4.2 Roberts, J. S . 3.8.3.7.1 Roberts, L. E. J. 3.10.1.4.1 3.10.1.4.2 3.10.3.1.3 3.10.1.3.1 3.10.3.1.2 3.10.2.3.4 3.10.3.1.1 Roberts. M. W. 3.10.1.2.2 3.10.1.2.3 3.10.1.3.1 3.10.1.3.3 3.10.1.4.1 3.10.1.4.2 3.10.1.5.3 3.10.1.5.4 3.10.3.1.1 3.10.3.1.2 3.10.3.1.3 Roberts, P. D. 3.7.2.2.2 Robinson. S . D. 3.8.2.7.2 3.8.3.4.2 3.8.3.4.3 Robinson, W. T. 3.8.2.6.1 Rode, W. C. 3.8.3.4.2 Rodionov. P. P. 3.8.2.4.2 Rodley, G. A. 3.8.2.6.1 Rodriguez-Lopez, J. L. 3.7.4.1.1 Roede, H. 3.11.6.1.2 Roesky, H. W. 3.7.4.6.2.7 Romer, M. 3.7.3.6 Rohrmann. J. 3.8.4 Rohwer, H. E. 3.8.2.6.1 Roland, E. 3.8.3.6.3 Rolandi. R. 3.11.5.1
337 Romashov, E. 3.8.2.9.1 Roof, L. C. 3.8.4 3.11.5 Roper, W. R. 3.8.2.1.2 3.8.4 Rosamilia. J. 3.10.3.2.1.1 Rosca, I. 3.8.2.10.1 Roseky, H. W. 3.8.3.4.2 Rosenberg. 0. 3.7.3.6 Rosenberg, R. C. 3.7.3.5.2 Rosenhein, L. D. 3.8.3.6.1 Rosenstein, G. 3.7.4.1.1 3.7.4.2.2 Rossing, A. 3.7.3.2 Roth. R. S. 3.10.1.2.3 3.10.1.5.5 3.10.2.3.3 3.10.3.2.1.5 3.10.3.4 3.10.3.4.1 3.10.3.4.2 Roth, S. 3.1 1.6.1.2 Rothwell, 1. P. 3.8.2.1.3 Rottman, R. 3.7.2.4.1 Roundhill, D. M. 3.8.2.6.3 3.8.3.6.2 Rouxel, J. 3.11.1 3.1 1.4.2 3.1 1.5.2 3.11.6 3.11.6.1.1 3.11.6.1.4 3.11.6.1.5 3.11.6.2 3.11.6.3 Rouxel, R. 3.11.6 Rowbottom, J. F. 3.8.3.4.2
338 Roy, M. 3.8.2.1.3 Roziere, J. 3.8.4 Ruchett, W. 3.11.2.1 Ruddlesden. S. N. 3.10.3.2.1.1 Rudlich, S. M. 3.1.3.6 Rudolph. G. 3.1.2.5 Riidorff. W. 3.11.5.2 3.11.6 3.1 1.6.1.1 Ruffing, C. J. 3.8.3.6.1 Ruh, R. 3.10.3.2.4.4 Ruiz, M. A. 3.8.2.1.3 Ruiz-Hitzky, E. 3.1 1.6.1.7 Rupp, H. 3.9.3 Rupp, J. J. 3.8.3.6.3 Rupp, L. 3.11.6.3 Rupp, Jr., L. W. 3.10.3.2.1.1 Ruschewitz, U. 3.11.6.4.1 Rutchik, S. 3.8.3.6.1 Ruthardt, R. 3.1 1.6.1.6 Ryan, J. L. 3.8.2.6.1 Rydon, H. N. 3.8.3.6.3 3.8.3.2.1 Ryzhenko, E. V. 3.7.4.1.1
S
Saak, W. 3.8.3.6.3 Saatkamp. K. 3.1.3.6 Sabat, M. 3.8.4 Sadanaga, R. 3.10.3.4 Sacconi, L.
Author Index 3.8.3.2.1 3.8.3.4.3 3.8.3.5.1 3.8.3.6.1 Sacerdoti, R. 3.7.4.1.1 Sadaoka, Y. 3.10.2.3.3 Sadasivan, N. 3.1.4.6.2.8 Sadler. P. J. 3.1.3.2 3.7.3.6 Sadowski, J. S. 3.7.2.2.2 Saeki, M. 3.11.3.2 3.11.4.2 Sager, R. S. 3.1.2.5 Sahajpal, A. 3.8.3.4.3 Sahle, W. 3.10.3.1.2 Saibene. S. 3.11.6.1.5 Said, F. F. 3.1.3.6 Saidi, M. Y. 3.10.3.2.2.3 3.10.3.2.4.5 Saiga, N. 3.8.4 Saito. T. 3.8.3.6.1 Sakaguchi, U. 3.7.3.3 Sakamoto, M. 3.10.2.3.3 Salazar, K. V. 3.8.2.7.1 Salifoglou, A. 3.8.3.6.1 Salmeron, M. 3.8.2.1.1 Salvemini, A. 3.1.2.2.2 Sanchez. L. 3.11.6.1.4 Sandbert, C. J. 3.10.2.2.1. Sanders, J. C. P. 3.9.3 3.9.4 Sanderson. R. T. 3.7.3.6
Sandhu. S. S. 3.7.4.6.2.6 Sandre, E. 3.11.6.1.1 Sandstrom, M. 3.8.2.2.2 Sandstrbm, M. 3.7.2.4.1 Sanger. A R. 3.8.2.4.2 3.8.2.4.3 Sano, Y. 3.11.6 3.11.6.4.1 Santa Ana, A. 3.1 1.6.1.l Santi, R. 3.7.2.4.2 Santini-Scampucci. C. 3.8.2.6.3 Sasaki, K. 3.1.4.6.2.4 Sasaki, Y. 3.8.2.2.1 Sata, H. 3.8.2.1.2 Satchell, D. P. M. 3.7.3.6 Satek. L. C. 3.7.4.6.2.6 Sato, M. 3.10.3.2.4.3 3.8.4 Satoh, S. 3.11.3.1 Satterfield. C. N. 3.1.2.3.1 Sauer, A. 3.8.2.1.3 Saux, M. 3.11.6.4.1 Saving, P. C. 3.1.3.4.2 Sawai, H. 3.7.2.1.2 3.8.2.1.2 Schafer, H. 3.10.3.5 SchBffer, H. 3.11.3.2 Scheider, S. J. 3.10.1.2.3 Scheidsteger. 0. 3.8.4 Schewe-Miller. I. 3.11.7.2
339
Author Index Schiff. A. 3.7.3.2 Schimanski. J. 3.7.3.6 Schimanski, U. 3.7.3.6 Schimek, G. L. 3.7.3.6 Schinco. F. P. 3.7.2.4.1 Schindler, J. L. 3.11.6.1.7 3.11.7.2 Schlanderbeck. H. 3.7.3.6 Schleede, k 3.7.4.5 Schleich, D. M. 3.8.3.6.1 Schlenker. C. 3.10.3.2.4.3 Schlesinger, H. I. 3.8.2.7.1 Schlogl, R. 3.7.2.1.1 Schlogl. R. 3.11.6.4.1 3.1 1.6.2 Schmalz, M. 3.11.6.2 Schmid. S. 3.10.1.5.5 Schmidbauer, H. 3.7.3.2 3.7.3.6 Schmidt, M. 3.8.4 Schmidtke, H. 3.7.4.5 3.7.4.6.2.7 Schmitt, M. 3.8.3.2.1 Schmitz, K. 3.7.3.6 Schmucker. W. 3.1 1.6.2 Schneider, S. J. 3.10.3.2.1.5 3.10.3.4 3.10.3.4.1 Schnering. H. G. 3.10.3.5 Schnock, M. 3.8.3.6.2 Schollhorn. M. 3.11.7.2
Schdllhorn, R. 3.10.3.2.4.1 3.11.5.1 3.11.6 3.11.6.1.1 3.11.6.1.2 3.1 1.6.1.5 3.11.6.1.6 3.11.6.1.7 3.1 1.6.2 3.11.6.4.1 3.11.6.4.2 Scholz. G. A. 3.11.6.1.2 Schrader, R. 3.7.4.1.1 Schramm. W. 3.11.6 3.1 1.6.4.1 3.11.6.4.2 3.11.7.2 Schrauzer. G. N. 3.7.3.5.1 3.7.3.6 Schrauzer. G. N. 3.8.3.5.1 Schreiber. Jr., H. 3.10.2.3.5 Schreiner, B. 3.7.4.6.2.1 Schreiner, F. 3.9.2 Schreiner, S. 3.8.3.6.2 3.8.4 Schrobilgen. G. J 3.9.2 3.9.3 3.9.4 Schrock, R. R. 3.8.3.6.3 Schrbder. M. 3.8.3.3 Schugar. H. T. 3.7.3.6 Schultz, B. E. 3.8.3.6.3 Schumacher. E. 3.9.3 Schumann, H. 3.8.4 Schumb, W. C. 3.7.2.3.1 Schussler. D. P. 3.7.3.3 3.8.3.4.2
Schwartz. C. 3.8.3.6.1 Schwartz, J. 3.8.2.1.3 Schwarz, W. H. E. 3.8.2.4.1 Schwarzhaus, K. E. 3.7.3.6 Schweitzer. k L. 3.10.3.3.5.4 Schwochau, K. 3.8.3.6.3 3.8.3.4.2 Scibona, G. 3.8.2.2.2 Scott. M. J. 3.8.3.6.3 Scott, N. 3.8.2.6.3 Scott. W. R. 3.10.2.3.3 Scovell, W. M. 3.7.4.6.2.7 Scudder, M. L. 3.7.3.6 3.7.4.6.2.1 3.7.4.6.2.3 3.8.4 Seeley, A. J. 3.7.3.7 Seff, K. 3.7.3.3 Segrist, T. 3.7.4.7 Seibert, 111. W. F. 3.8.2.1.3 Seidel, W. C. 3.7.3.4.2 Seigneurin. A. 3.8.4 Sekiguchi, Y. 3.8.3.6.3 Sekikawa. Y. 3.10.3.3.2 Selig, H. 3.9.2 Seligson. k L. 3.7.4.6.2.4 Sellrnann, D. 3.8.3.6.3 Selte. K. 3.11.6.4.1 Selvyn, L. S. 3.11.6.4.2 3.11.6.4.2 Senftle. F. E.
340
Senftle, F. E. (Continued) 3.7.3.6 Sennikova, G. V. 3.7.2.3.2 3.8.2.3.1 Seppelt. K. 3.9.3 3.9.4 Sepulchre, M. 3.7.2.2.2 Spassky, N. 3.7.2.2.2 Sergeeva, L. A. 3.7.4.5 Sergent, M. 3.11.6 3.11.6.3 3.1 1.6.4.2 3.11.7.2 Serhadli, 0. 3.8.4 Sermage, B. 3.7.4.7 Serna, C. J. 3.10.2.3.1 Setton, R. 3.11.6.4.2 Severson, R. G. 3.8.2.8.2 Shackelford, S. A. 3.9.2 Shackleton, S. S. 3.7.3.6 Shafer, M. W. 3.1 1.6.1.2 3.1 1.6.1.3 3.1 1.6.1.5 3.1 1.6.1.6 Shakshooki, S. K. 3.8.2.6.1 Shannon, R. D. 3.10.3.1.1 Shanton, K. J. 3.8.4 Shapkin, G. N. 3.9.4 Shapley, P. A. 3.8.3.6.1 3.8.3.6.3 Sharma, R. 3.10.3.3.1 Sharma, R. D. 3.7.4.6.2.2 Sharp, D. W. A. 3.8.2.10.1 Sharpe, A G.
Author Index 3.7.2.1.1 3.7.4.1.1 3.8.2.1.1 Shatalov, G. V. 3.8.2.10.1 Shaver, A. 3.8.3.6.1 3.8.3.6.2 Shaw, F. 3.7.3.2 Shaw, G. 3.7.4.1.1 3.7.4.1.2 Shawl, E. T. 3.7.3.5.1 Shchastlivyi, V. P. 3.7.4.1.1 3.7.4.1.2 3.7.4.2.1 3.7.4.3 3.7.4.4 3.7.4.5 Shearer, H. M. M. 3.7.3.2 Sheldrick, G. M. 3.7.4.6.2.1 Sheldrick, W. S. 3.8.3.6.1 3.8.3.6.2 3.8.4 3.11.5.1 Shellhamer, D. F. 3.9.2 Sherwood. R. C. 3.10.3.2.1.1 Sheshadri, R. 3.10.3.2.1.1 Shevlin, P. B. 3.8.3.7.1 Shi. H. 3.10.3.2.4.5 3.10.3.2.2.3 Shibahara, T. 3.8.3.6.1 3.8.3.6.3 Shiever, J. W. 3.11.3 Shikano, M. 3.10.3.2.1.1 Shimura. R. 3.10.3.2.1.1 Shiraishi, T. 3.11.3.1 Shoesmith, D. W. 3.11.5.1 3.1 1.6.3
Shoner. S. C . 3.8.3.6.3 Shriver, D. F. 3.10.3.2.2.2 Shulz, K. H. 3.7.2.1.3 Shumacker. G. k 3.9.3 Shushunov. V. A. 3.7.2.1.3 3.7.2.3.1 Sick, E. 3.1 1.5.1 3.11.6.1.5 Sidgwick. N. V. 3.7.3.1.1 3.7.3.2 3.7.3.3 3.8.3.1.1 Sidorov, M. 3.11.6.1.2 Siegrist, H. T. 3.10.3.2.1.1 Siegrist, T. 3.10.3.3.1 Siemeling. U. 3.7.4.6.2.3 Siemelung, U. 3.7.4.6.2.4 Siemons. W. J. 3.7.3.1.1 3.7.4.1.1 Sienko, M. 3.10.3.3.3 Sievers, R. E. 3.8.2.7.1 Sigel. H. 3.7.2.1.2 3.7.3.2 Silbernagel, B. G. 3.11.6.1.7 Simhan, E. 3.7.3.2 Simhon, E. 3.7.3.6 3.8.3.2.1 3.8.3.6.3 Simhon, E. D. 3.8.3.6.1 Simon, W. 3.8.4 Simopoulos, A. 3.7.3.2 3.8.3.6.1 Simpson, W. I. 3.7.4.7
Author Index Singh. 0. 3.11.6.1.5 Singh, H. B. 3.7.4.7 Singh, J. V. 3.8.2.4.1 Sinha, S. 3.11.6 3.11.6.4.2 Sinn, E. 3.8.4 Skarnulis, A. J. 3.10.3.1.3 Skell, P. S. 3.8.3.7.1 Skopenko, V. V. 3.7.4.6.2.7 Skovlin, D. 0. 3.8.2.4.1 Skraba, Z. 3.11.6 Skurlatov. Y. I. 3.7.2.3.1 Sladek, k 3.7.3.6 Sladky, F. 3.9.3 Sladky, F. 0. 3.9.1 3.9.3 Slaven, R. W. 3.7.2.1.2 Sleight, A. W. 3.8.3.2.1 3.10.3.5 3.10.3.3.1 Slick, P. I. 3.10.2.3.5 Smart, L. E. 3.8.2.6.2 Smirnova, R. N. 3.7.4.4 Smith, D. F. 3.9.2 Smith, D. M. 3.8.4 Smith, F. 3.8.2.7.1 Smith, J. A 3.8.3.2.2 Smith, J. N. 3.8.3.4.2 Smith, K. P. 3.8.2.1 1.3 Smith, R. M. 3.7.2.7.1
3.8.2.9.1 Smyth, D. M. 3.10.2.3.1 3.10.2.3.3 Sneed, M. C. 3.7.2.2.1 Snyder, B. S. 3.8.3.6.1 SO.J.-H. 3.8.3.6.1 Sobczak, R. 3.11.6.2 Sola, J. 3.8.3.6.1 Solans, X 3.8.3.4.3 Soled, S. 3.11.7.1 Solin, S. A. 3.11.6.1.2 Sollmann. K. 3.11.6 Solombet, P. 3.11.6.1.6 Solomon, E. I. 3.7.2.1.2 Somerjai, G. A 3.8.2.1.1 Sommer, H. 3.7.3.2 Somoano. R. B. 3.11.6.1.1 Sonnino, T. 3.9.4 Sorensen, 0. T. 3.10.1.2.1 3.10.1.5 3.10.2.2.1. 3.10.2.2.3 Sosnowsky, G. 3.7.2.1.3 Sourisseau, C . 3.11.6 3.11.6.3 Southern, T. G. 3.8.3.6.3 Sovago, I. 3.7.3.2 Sowerby. D. B. 3.8.3.4.2 Spandau, H . 3.7.2.6.1 3.8.2.8.1 3.8.2.8.3 Spencer, J. L. 3.8.2.6.2
341 Spencer, N. 3.7.3.6 Spinelli. D. 3.7.2.2.2 Spittler, T. M. 3.9.2 Spitzli, P. 3.11.7.2 Spofford, 111, W. k 3.7.3.3 Sprinkle, C . R. 3.7.4.6.1.2 3.7.4.7 3.8.4 Sproull, R. L. 3.10.2.1 Spychiger, H. 3.1 1.2.2 Sritharan, S. 3.7.4.7 Srivastava, P. C. 3.7.4.6.2.2 Srivastava, R. C. 3.8.2.4.2 Stacy, A. M. 3.1 1.6.1.1 Stafford, P. R. 3.8.3.6.3 Stage, M. E. 3.8.2.4.2 Stalhandske, C. 3.7.4.6.2.8 Staples, R. J. 3.1.3.2 3.7.3.5.1 Starnberg, H. I. 3.11.6 Steele, R. M. 3.10.3.5 Steggerda. J. J. 3.7.3.4.1 3.8.3.4.1 3.8.3.4.2 Steigerwald. M. L. 3.7.4.7 3.7.4.6.2.4 3.8.4 Stephan, D. W. 3.8.3.6.3 Stephenson, N. C . 3.10.3.2.4.3 3.10.3.4.2 Stem, C. L. 3.7.3.6 3.7.4.6.1.2 3.8.4
342 Stetter, K. H. 3.7.3.6 Steudel, R. 3.8.3.6.3 3.8.4 Stevels, A L. N. 3.7.4.1.1 Stevens, R. A. 3.1 1.5.1 Stiefel. E. I. 3.1.3.5.2 3.8.3.2.2 Stocco, F. 3.7.4.6.2.7 Stocco, G. 3.7.4.6.2.7 Stoklasa, H. J. 3.8.3.4.2 Stoklosa, H. J. 3.1.3.4.1 Stone, F. G. A. 3.8.2.6.1 3.8.2.6.2 Strasdeit. H. 3.8.3.6.2 Stoneham, A. M. 3.10.1.2.3 Strahle, J. 3.7.3.6 3.10.3.1.3 Strakhov, L. P. 3.1.4.5 Strasdiet, H. 3.8.4 Straws, S. H. 3.8.3.4.2 Stremple. P. 3.1.3.2 3.7.3.6 3.8.3.6.3 3.8.3.2.1 Streng, A. G. 3.9.4 Strickler, P. 3.1.3.6 Strobel, P. 3.10.3.2.2.3 Struchkov, Yu. T. 3.8.3.6.3 Stucky. G. D. 3.1 1.5.1 Stuczynski, S. M. 3.1.4.6.2.4 3.7.4.1 Stlidemann, T. 3.7.3.1.2
Author Index Studer, F. 3.10.3.3.5.1 Su, A. C. L. 3.8.2.7.1 Subbarao, E. C. 3.10.3.2.1.3 Sudha, N. 3.7.4.1 Sugawara, T. 3.1.4.6.2.4 Suge, I. 3.7.4.1.1 3.7.4.1.2 Sugimoto, M. 3.10.2.3.5 Sugiura, Y. 3.1.4.6.2.1 Sugiyama, J. 3.10.2.3.1 Sullivan, J. F. 3.8.3.4.2 Summerville, D. A 3.8.2.1.2 Sun, Z. 3.8.3.6.1 Sundberg, M. 3.10.1.3.2 3.10.1.3.3 3.10.3.1.2
Sunshine, S. A.
3.8.3.6.2 3.1 1.6.1.1 Sutcliffe, R. 3.7.2.1.1 3.7.2.8 Sutorik, A. 3.7.3.6 Sutorik, A. C. 3.8.3.6.1 3.8.3.6.2 3.8.4 Suzuki, K. 3.1 1.6.1.4 Svensson, G. 3.10.3.3.1 Swalin. R. A. 3.11.3.1 Swenson, D. 3.7.3.1.2 3.7.3.2 3.7.3.6 Swern, D. 3.7.2.3.1 Syamal, A. 3.8.2.1.1 Syassen, K.
3.10.3.2.1.1 Sykes, A. G. 3.7.2.1.2 3.8.2.1.2 3.8.2.2.1 3.8.2.2.2 3.8.3.6.1 Sylva, R. N. 3.8.2.2.2 Sysoeva, N. P. 3.8.2.4.2 Syvret, R. B. 3.9.2 Syvret. R. G. 3.9.3
T
Tabachenko, V. V. 3.10.1.3.2 3.10.1.3.3 Tacon, J. 3.8.2.7.1 Tadros, S. 3.1.3.6 Tainturier, G. 3.8.4 Tait. A. M. 3.7.2.1.2 Takacs, J. 3.8.3.6.1 Takeuchi, Y. 3.10.3.4 Takeuchi, Y. 3.10.1.3.3 Takizama. T. 3.7.2.1.2 3.8.2.1.2 Tamai. Y. 3.7.4.6.2.7 Tan, A. L. 3.8.3.6.1 Tan. L.-C. 3.7.3.6 Tanaka, H. 3.1.3.5.1 3.1.4.6.2.1 Tanaka, K. 3.7.4.1 3.8.3.6.1 Tanaka, M. 3.10.2.3.1 Tanaka, S. 3.8.4 Tanaka. T. 3.7.4.6.2.9 Tanaka, Y.
Author Index 3.7.2.8 Tane-ichi. S. 3.8.2.4.2 Tang. K. 3.7.3.6 Tang. S. C. 3.8.3.6.3 Tang. Y. 3.1.3.6 Taniguchi, A. 3.8.3.6.1 Taogoshi, G. J. 3.8.3.6.1 Tarascon, J. M. 3.11.6 3.11.6.3 3.11.6.4.2 Tarte, P. 3.10.3.3.3 Tasker, P. W. 3.10.1.2.3 Tatsumi. K. 3.8.3.6.1 3.8.3.6. Taube, H. 3.8.2.2.1 3.8.3.6.3 Taubenest. R. 3.9.3 Taylor, A. 3.10.2.2.1. Taylor, D. 3.7.2.4.1 3.8.3.4.2 Taylor, K. A. 3.8.2.9.1 3.8.2.9.2 Taylor, N. J. 3.7.4.6.2.7 Taylor, P. 3.11.5.1 3.11.6.3 Taylor, R. I. 3.10.1.2.1 Tebbe, F. N. 3.8.3.4.2 Tejuca, L. G. 3.10.2.3.3 Teo. B. K. 3.1 1.6.3 ter Haar, L. W. 3.11.6.4.2 Teraski, 0. 3.10.2.2.1. Terauchi, H. 3.10.2.2.1.
Thackery, J. R. 3.8.3.4.2 Thery, J. 3.10.3.2.2.2 Thewalt, U. 3.8.4 Thieffry, C. 3.11.6.3 Thoden, J. B. 3.8.4 Thomas, I. M. 3.8.2.4.2 3.8.2.4.3 Thomas, J. K. 3.10.3.2.1.3 Thomas, J. M. 3.10.1.2.2 3.10.1.2.3 3.10.1.3.1 3.10.1.3.3 3.10.1.4.1 3.10.1.4.2 3.10.1.5.3 3.10.1.5.4 3.10.2.3.3 3.10.3.1.1 3.10.3.1.2 3.10.3.1.3 Thomas, P. 3.8.3.4.2 Thompson. A. 3.8.2.6.3 Thompson, A. H. 3.11.6.1.7 Thompson, A. J. 3.11.6.1.6 Thompson, D. Y. 3.8.2.9.1 Thompson, J. G. 3.10.1.5.5 Thompson. J. S. 3.7.3.6 Thompson, L. D. 3.7.3.3 Thompson, P. J. 3.1.3.2 Thone. C . 3.7.4.6.2.6 3.7.4.6.2.7 3.7.4.6.2.9 Thoni. W. 3.11.2.2 Thorez. A. 3.8.3.6.3 Thorn. G. D. 3.7.3.4.1
343 3.8.3.4.2 Thornton. P. 3.8.2.4.2 Tibbals, C. k 3.7.4.6.2.1 Tilley, R. J. D. 3.10.1.2.2 3.10.1.2.3 3.10.1.3.1 3.10.1.3.2 3.10.1.3.3 3.10.1.4.1 3.10.1.4.2 3.10.1.5.4 3.10.2.3.2 3.10.3.1.1 3.10.3.1.2 3.10.3.1.3 3.10.3.3.5.1 Timms, P. L. 3.7.3.7 3.8.2.11.1 3.8.3.7.1 Tirado, J. L. 3.11.6.1.1 3.1 1.6.1.4 Tishchenko, G. N. 3.7.4.1.1 Tissue, P. 3.7.2.1.1 Tobe. M. L. 3.8.2.2.1 Tobias, R. S. 3.7.4.6.2.1 Tofield, B. C. 3.10.2.3.3 Togano, K. 3.10.3.2.1.2 Togashi, S. 3.8.2.11.1 3.8.3.7.1 Tomietto, M. 3.7.3.7 Tominaga, Y. 3.8.3.6.1 Toriumi, K. 3.10.3.2.4.3 Toropova, M. A. 3.9.4 Tosatti. E. 3.11.6.1.2 3.11.6.4.1 Toscano, P. J. 3.8.2.1.3 Toupadakis, A. 3.8.3.6.1
Author Index
344 Tourangeau, M. C. 3.7.4.6.2.1 Tournoux, M. 3.10.3.2.1.5 3.10.3.3.2 Touxel, J. 3.1 1.6.1.1 Towle, I. D. H. 3.8.2.4.2 Tranquille, M. 3.8.2.11.3 Trautwein, A. X 3.1.3.6 Traversa, E. 3.10.2.3.3 Tremillon. B. 3.11.6 Trevor, D. J. 3.8.2.1.1 Treyvaud, A. 3.11.7.2 Tributsch, H. 3.1 1.6 Trichet. L. 3.11.5.2 3.11.6 3.11.6.1.1 Trifona, E. 3.1.4.2.1 Trigchelaar, D. 3.11.6.1.1 Trotman-Dickenson, A. F. 3.7.4.2.1 3.7.4.3 3.7.4.5 3.9.1 Trumbore, F. A. 3.1 1.6.3 Tsaegusa, T 3.7.2.1.1 3.1.2.1.2 Tsai, H. L. 3.11.7.2 Tsang, J. C. 3.1 1.6.1.5 3.11.6.1.7 Tse, J. S. 3.7.3.7 Tsintsadze, G. V. 3.7.4.6.2.1 Tsuchida. E. 3.8.2.1.2 Tsuda, T. 3.1.2.7.1 3.7.2.7.2 Tsutsui, M.
3.7.2.6.3 3.8.2.4.1 Tuck, D. G. 3.7.3.6 3.1.4.6.1.2 Turner, J. J. 3.7.2.8 3.8.2.11.3 3.9.2 Turowsky, L. 3.9.3 Turtan. L. M. 3.8.2.7.1 Tutton. A. E. H. 3.7.4.5 Tyree, S. Y. 3.8.2.6.3 Tyrra, W. 3.9.2 3.9.3 Tyrziu, V. G. 3.7.4.1.1 3.7.4.1.2
U
Uchida, T. 3.10.2.3.1 Uelsman, H. 3.7.4.3 Ueyama, N. 3.7.4.6.2.4 3.8.3.6.3 Uhlig. E. 3.8.2.6.1 Uppal, M. K. 3.10.2.3.3 Urichemeyer, E. 3.8.4 Usachev. P. V. 3.7.4.1.1
V Vamanaka, T. 3.1 1.3.1 van Bolhuis, F. 3.11.6.1.2 van Bruggen, C. F. 3.11.1 3.11.2.1 3.11.6 3.1 1.6.1.1 Vance, B. 3.8.3.5.1 3.8.3.5.2 van Daalen. J. 3.8.2.7.1
van den Hurk, J. W. G. 3.1.2.5 Van der Linden, J. G. M. 3.7.3.4.1 3.7.3.5.2 van der Meer, R. 3.11.6.1.5 Van der Roer. H. G. J. 3.7.3.5.2 VanDoorne, W. 3.8.3.6.1 van Dyck, D. 3.11.6.1.2 Van Gool, W. 3.10.3.4.2 van Heiningen. H. 3.11.6.1.5 van Heyningen, T. C. 3.7.2.5 van Heyningen. Th. C. 3.8.2.7.1 van Laar. B. 3.11.4.2 van Landuyt, J. 3.1 1.6.1.2 Van Leirsburg, D. A. 3.8.2.11.3 Vannerberg, N. G. 3.1 1.6.2 Van Poucke, L. C . 3.7.3.2 Van Smaalen, S. 3.10.1.5.5 3.10.3.2.4.3 Van Tendeloo, G. 3.10.3.2.1.2 3.11.6.1.2 Van Zee. R. J. 3.8.2.1.1 Vasanthacharyaa, N. Y. 3.7.3.6 Vaska, L. 3.8.2.1.2 Veal, B. W. 3.10.3.2 3.10.3.2.1.2 Veale. C. R. 3.7.4.1.1 3.7.4.1.2 Veblen. D. R. 3.10.1.4.1 3.10.1.4.2 Venturelli, A. 3.8.3.6.1 Verbeak. F. 3.7.2.5
345
Author Index Vergamini. P. J. 3.8.3.2.3 3.8.3.6.2 Verma, k D. 3.7.3.6 Verma, A K. 3.8.3.6.2 3.8.3.6.3 Verschoor, G. C. 3.7.3.6 Verwey, E. J. 3.10.2.3.1 Viccary, M. W. 3.10.3.1.3 Villafaiie, F. 3.8.2.1.3 Vincente, J. 3.8.2.1.3 Viola, F. 3.11.6.2 Vitrikhovskii, N. I. 3.7.4.1.1 Vittal, J. J. 3.7.4.6.2.3 Vlasse, M. 3.11.6.4.1 Voet, A Vander 3.8.2.11.3 Vogel, E. M. 3.10.2.3.5 Volkov, B. L. 3.10.3.2.4.1 3.10.3.3.4 Volosatova, N. S. 3.7.4.1.1 Volpin, M. E. 3.7.2.6.3 Von Dreele, R. B. 3.8.2.7.1 3.10.2.2.2 3.10.3.1.3 Vonk, M. W. 3.7.2.5 3.8.2.7.1 von Schnering. H. G. 3.11.6.2 von Wesendonck. C. 3.11.6.1.5 Vorres. K. 3.10.3.5 Vortisch. V. 3.7.3.6 Vurens, G. H. 3.8.2.1.1 Vyshinskaya. L. I 3.8.2.10.1
W
Wachold, M. 3.8.3.6.2 3.8.4 Wachter, J. 3.8.4 Wachter, P. 3.11.1 3.1 1.2.2 Waddington. T. C. 3.8.2.10.1 Wade, K. 3.7.2.2.2 Wadsley, k D. 3.10.1.3.1 3.10.1.3.2 3.10.1.5.4 3.10.3.1.3 3.10.3.2. 3.10.3.2.1.3 3.10.3.2.4.3 3.10.3.2.4.4 3.10.3.2.4.6 3.10.3.3 3.10.3.3.1 3.10.3.3.2 3.10.3.3.3 Wails, P. C. 3.8.2.6.2 Wakatsuki, Y. 3.7.4.6.2.4 Wakihara. M. 3.10.2.3.1 Walborsky, E. C . 3.8.3.6.3 Walf, E. 3.11.2.1 Walker. A. 3.8.4 Walker, E. 3.1 1.7.2 Walker, J. M. 3.7.4.6.2.4 Walsh, M. 3.11.6.3 Walther, D. 3.8.2.6.1 Walters. M. A. 3.8.3.6.1 Walton, E. D. 3.7.4.6.2.6 Wang, C. C. 3.10.3.3.5.1 Wang, E. 3.10.3.3.3 3.10.3.3.5.1
Wang, J. S. 3.10.3.3.5.4 Wang, R. 3.8.2.1.3 Wang, S. L. 3.10.3.3.5.1 Wang. Y. 3.7.3.6 3.11.5.1 Ward, R. 3.10.2.3.3 Wardlaw, W. 3.8.2.4.2 Wardle, R. W. M. 3.8.4 Waring. J. L. 3.10.3.4 3.10.3.4.1 3.10.3.4.2 Warner, L. G. 3.7.3.3 Wasson. F. J. 3.8.3.4.2 Wasson. J. R. 3.7.3.4.1 Waszczak. J. V. 3.10.3.2.4.1 3.10.3.3.2 3.11.5.2 3.11.6 Watanabe. D. 3.10.2.2.1. Watanabe, M. 3.10.3.3.2 Watkins, P. M. 3.8.3.4.2 Watson. A. D. 3.8.3.6.3 Watson, W. H. 3.7.2.4.1 3.7.2.5 Weatherill. T. D. 3.8.3.6.1 3.8.3.6.3 3.8.4 Webb. K. 3.7.4.7 Webb. K. J. 3.1.4.6.1.2 3.7.4.6.2.2 3.7.4.6.2.3 3.7.4.7 Webb, T. R. 3.8.3.7.1 Weber, K. L. 3.7.4.6.2.1
346 Wechsberg, M. 3.9.3 Wei, C . 3.8.4 Wei, L. 3.8.3.2.2 Weichselbaumer, G. 3.8.3.6.2 Weigel, J. A. 3.8.3.6.3 Weigold, H. 3.8.2.6.2 Weiher, J. F. 3.8.2.7.1 Weil. J. k 3.8.2.1.2 Weininger, M. S. 3.7.3.3 Weiss, A. 3.7.2.5 3.11.6.1.5 3.11.6.1.6 3.11.6.1.7 3.11.6.2 3.11.7.2 Weiss, E. 3.8.4 Weiss, J. 3.8.3.6.1 Weiss, R. 3.7.2.1.2 3.8.2.7.1 3.8.3.2.1 Welch, A. J. 3.7.3.3 Weller, F. 3.7.2.2.2 3.8.4 Weller, M. T. 3.10.3.2.1.1 Wells, A. F. 3.7.3.1.1 3.10.3.2 3.10.3.2.2.1 3.10.3.3 3.10.3.3.1 3.10.3.3.3 3.10.3.4.3 Weltner, Jr.. W. 3.8.2.1.1 Wentworth. R. L. 3.7.2.3.1 Werner, H. 3.8.2.1.3 3.8.4 Wernicke. R.
Author Index 3.10.2.3.1 Wessner, D. 3.8.2.7.1 West. A. R. 3.10.3.2 West, K. W. 3.8.4 Westphal, U. 3.8.3.6.3 Whalen, J. M. 3.9.3 Whangbo. M.-H. 3.10.3.3.5.1 3.11.6.1.1 3.10.3.3.5.1 Whelan, J. 3.7.3.6 Whetten, R. L. 3.8.2.1.1 White, A. H. 3.7.2.4.1 3.7.3.3 3.8.3.4.2 White, P. S. 3.8.4 3.8.2.1.3 White, R. E. 3.11.6 Whitesides. G. M. 3.7.2.2.2 Whitingham. M. S . 3.11.6.3 Whitmire, K. H. 3.8.4 Whittaker. B. 3.8.2.6.1 3.8.2.7.1 Whittingham. M. S. 3.10.2.3.4 3.10.3.2.4.1 3.10.3.2.4.2 3.11.6 3.11.6.1.1 3.11.6.1.5 3.11.6.1.7 3.11.6.2 Wiberg. E. 3.11.6 Wiechmann, F. 3.8.3.1.1 Wiegers. G. A. 3.1 1.4.2 3.11.6 3.1 1.6.1.1 3.11.6.1.2 3.11.6.1.4
3.11.6.1.5 Wieghardt, K. 3.8.3.6.1 Wijsman, A. J. M. 3.7.2.5 3.8.2.7.1 Wiley. J. B. 3.8.3.6.1 Wilk, A. 3.8.4 Wilke. G. 3.8.2.4.2 Wilkins. C. J. 3.8.2.6.1 Wilkins. R. G. 3.8.2.1.2 3.8.2.2.1 Wilkinson, A. J. 3.8.2.11.3 Wilkinson, G. 3.7.2.1.1 3.7.2.2.2 3.7.3.1.1 3.7.3.2 3.7.3.6 3.8.2.1.1 3.8.2.2.1 3.8.2.2.2 3.8.2.3.1 3.8.2.4.2 3.8.2.4.3 3.8.2.6.2 3.8.2.10.1 3.8.3.1.1 3.8.3.4.2 3.8.3.5.1 3.8.3.6.1 3.8.3.6.2 Wilkinson, J. L. 3.7.2.1.2 Wilkinson, M. K. 3.10.3.5 Willemse. J. 3.7.3.4.1 3.1.3.5.2 3.8.3.4.1 3.8.3.4.2 Willett. G. D. 3.7.3.6 Williams, D. 3.8.3.4.2 Williams. H. J. 3.10.3.2.1.1 Williams, L. E. 3.7.4.6.2.1 Williams. R. P.
347
Author Index 3.10.3.1.3 Williams-Smith, D. L. 3.8.3.7.1 Williamson. S. M. 3.9.2 Willis, B. T. M. 3.10.1.2.1 3.10.2.2.3 Wilson, S. R. 3.7.3.6 3.8.3.6.1 3.8.3.6.2 3.8.3.6.3 3.8.4 Wilson, W. W. 3.9.2 Windsell. W. E. 3.8.4 Winkler, F. K. 3.7.3.6 Winter. G. 3.8.2.10.1 Wirl, A. 3.8.4 Wiswanathan, R. 3.10.3.2.2.3 Withers, R. L. 3.10.1.5.5 Woff, T. E. 3.8.3.2.1 Wojcicki, A. 3.8.2.7.2 3.8.2.8.2 Wolczanski, P. T. 3.8.2.1.3 Wold. A. 3.7.2.1.1 3.8.2.1.1 3.10.3.2.4.1 3.10.3.2.4.3 3.10.3.3.4 3.11.7.1 Wolf, E. 3.11.3.2 3.11.1 Woltermann. G. M. 3.7.3.4.1 3.8.3.4.2 Wong, J. 3.8.2.1.2 Wong, V. K. 3.8.4 Wood, J. 3.11.6.2 Wood, P. T. 3.7.3.6
3.8.4 Woodbridge, D. T 3.7.4.6.2.5 Woods, L. A. 3.7.3.2 Woodward, P. G. 3.8.3.6.3 Woolam, J. A. 3.1 1.6.1.1 Woolins, J. D. 3.8.3.1.1 Worner, E. 3.11.6.4.1 Worrell. W. L. 3.11.6.1.1 Wrigge, W. 3.7.4.2.1 Wright. D. B. 3.7.3.6 Wright. P. J. 3.7.4.7 Wulfsberg, G. 3.7.2.5 Wunderlich. H. 3.7.4.2.2 Wypych. F. 3.1 1.6
X
Xu, J. 3.10.3.3.5.2
Y
Yaghi, 0. M. 3.8.3.6.1 Yakel. H. L. 3.10.3.5 Yakhmi, J. V. 3.10.3.2.1.2 Yamada, A. 3.10.2.3.1 3.11.6.1.1 Yamada, E. 3.11.5.2 Yamada. Y. 3.8.3.6.3 Yamaga, S. 3.7.4.7 Yamamoto, A. 3.8.2.4.2 Yamamoto, H. 3.8.2.1.2 Yamamoto. S . 3.8.2.7.2 Yamamoto. T. 3.8.2.4.2
3.8.2.7.2 3.8.3.6.1 3.1 1.6.1.1 Yamashita, S. 3.7.4.6.2.4 Yamazaki. H. 3.7.4.6.2.4 3.8.2.5.1 Yan, J. 3.11.4.2 Yan, M. F. 3.10.2.3.5 Yanaki, A. A. 3.11.4.1 3.11.4.2 Yang, D. 3.11.5.2 3.11.6.1.7 Yang, 0. 3.7.3.6 Yangming, S. 3.7.2.1.1 Yanovskaya. I. M. 3.1 1.6.1.5 Yao, X. 3.1 1.7.1 Yao, Y. F. Y. 3.10.3.2.2.2 Yarovoi, S. S. 3.8.3.6.1 Yasuoka, N. 3.7.4.6.2.4 Yoffe, A. D. 3.11.6.1.1 3.11.6.1.3 Yoffe. G. D. 3.1 1.6.1.2 Yokoyama. A. 3.7.3.5.1 Yonetani. T. 3.8.2.1.2 Yoshida, T. 3.8.4 Yoshikawa. A. 3.7.4.7 YOU,J.-F. 3.8.3.6.1 3.8.4 Yougfa, 2. 3.7.2.1.1 Young, D. M. 3.7.3.6 Young. G. B. 3.8.2.4.2 3.8.2.4.3 3.8.2.10.1
348 Young, H. S. 3.7.4.1.1 Yu,K.-M 3.7.4.6.2.4 Yukimasa, H. 3.7.2.1.2 3.8.2.1.2 Yun. S. S. 3.8.3.7.1 Yvon, K. 3.11.6.4.2
Z
Zachariasen, W. H. 3.10.3.2.2.3 Zagefka. H. D. 3.11.6.1.6 Zahurak, S. M. 3.10.3.3.2 3.1 1.6.1.1 Zaima, H. 3.8.3.6.3 Zandbergen, H. W.
Author Index 3.10.3.2.1.1 Zanello, P. 3.8.3.6.1 Zank, G. A. 3.8.3.6.1 3.8.3.6.2 Zars-Adarni, N. 3.8.3.4.2 Zelenski, C. M. 3.11.5.1 Zeta, J. 3.7.3.3 Zhang. J. 3.10.2.2.2 Zhang. Y. 3.8.3.6.1 Zhao, B. 3.8.2.1.3 Zhao, J. 3.7.4.6.2.8 Zhao, X. K. 3.1 1.5.1 Zhou. 0. 3.10.3.2.1.1 Zhou. X.
3.11.6.1.7 Ziegler, M. L. 3.8.4 Zimmermann. M. 3.7.3.6 Zingaro. R. k 3.7.4.6.2.7 Zintl, E. 3.7.4.1.1 3.7.4.1.2 Zintl, F. 3.7.4.6.2.8 Zoellner, R. 3.7.2.8 Zuberbuhler, A. D. 3.7.2.1.2 Zubieta, J. 3.7.3.6 3.7.3.5.2 3.10.3.3.5.4 Zubieta. J. A. 3.8.3.2.1 3.8.3.4.2 zur Loye, H.-C. 3.10.3.2.1.3
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
Compound Index This index lists individual, fully specified compositions of matter that are mentioned in the text. It is an index of empirical formulas, ordered according to the following system: the elements within a given formula occur in alphabetical sequence except for C, or C and H if present, which always come first. The formulas are ordered alphanumerically without exception. The index is augmented by successively permuted versions of all empirical formulas. As an example, C3H3Al09 will appear as such and, at the appropriate positions in the alphanumeric sequence, as H3*C3Al09, Al*C3H309 and 09*C3H3Al. The asterisk identifies a permuted formula and allows the original formula to be reconstructed by shifting to the front the elements that follow the asterisk. Whenever an empirical formula does not show how the elements are combined in groups, it is followed by a linearized structural formula, which reveals the connectivity of the compound(s) underlying the empirical formula and serves to distinguish substances which are identical in composition but differ in the arrangement of elements. The nonpermuted empirical formulas are followed by keywords. They describe the context in which the compounds represented by the empirical formulas are discussed. Section numbers direct the reader to relevant positions in the book. A Ag Ag active metal powder: 3.7.2.8 catalysis of ethylene oxidation: 3.7.2.1.3 AgAsF6 AgAsF6 starting material in formation of [Ag2(Ph2Se2)4][AsF6]: 3.7.4.5.2 AgBF4 AgW41
350
Compound Index
Ag*Ci4H2oNOs Ag*C i 8H20BF402 Ag*Ci 8H36hN209S Ag*CzoHzoFioNSz Ag*C24H2oPSe4 Ag*C96HsoTe12 Ag*H404AgNO3 formation from Ag and N204: 3.7.2.6.1 reaction of 3.7.3.6 reaction with benzo-15-C-5: 3.7.2.5.1 reaction with H2S: 3.7.3.2 Ago Ago formation: 3.7.2.1.1 Ago [AgIAgIJ102] formation from [Ag(OH)4]- and KOH: 3.7.2.7.2 Ago2 Ag[Ozl matrix isolation: 3.7.2.8 Ago2 Ag(q2-02)(matrix-isolated species) formation: 3.7.2.1.1 Ago4 AgD41 matrix isolation: 3.7.2.8 AgSSi Ag-SiS matrix isolation: 3.7.2.8 AgS$ [Ag(S4)213formation: 3.7.3.6 AgS9AgS9formation: 3.7.3.6 Ag2*C32H~Se4W Agz*C48H40AszF1zSes A~~*C~OHXS’JZS~ Ag2O Ag20 formation: 3.7.2.1.1 starting material: 3.7.4.4.1 Ag204Se AgzSeO4 formation: 3.7.4.4.2 AgzO4Te AgzTeO4 formation: 3.7.4.4.2 Ag2S Ag2S exchange reaction: 3.7.4.2.1 formation: 3.7.3.1.1
formation: 3.7.3.6 formation from Ag and SO2: 3.7.2.6.1 solubility: 3.7.3.2 Ag2S0.1 Ag2S04 formation from Ag and S02: 3.7.2.6.1 Ag2Si22[Agz(S6)212formation: 3.7.3.6 AgzS204[AgdS20)14formation: 3.7.3.6 Ag2Se Ag2Se formation: 3.7.4.1.1 formation: 3.7.4.2.1 formation: 3.7.4.3.1 AgtTe AgzTe formation: 3.7.4.1.2 formation: 3.7.4.1.3 formation: 3.7.4.2.1 formation: 3.7.4.3.1 formation: 3.7.4.4.1 formation from polychalcogenide: 3.7.4.6.2.1 Ag3*C3oH91S3Sis Ag3*CmH45S3Sis Ag3NOsTe AgzTeO3 AgN03 formation: 3.7.4.2.1 Ag4*C6Hi2N2Sei2 Ag4*C8Hl6AU2S82A~~*CBH~ON~S~I~ Ag4*C4oHiosS4Si12 Ag4*C72H58P2S6Te6 Ag5*C42hW[Ag5S31formation: 3.7.3.6 Ag6*C48H4oS82AggS42[Ag6S4I2formation: 3.7.3.6 Ag7S4[Ag7S41formation: 3.7.3.6 AmTed Ag7Te4 Ag-Te system: 3.7.4.1.2 &B*CBOH216SBSi24 Ag9*C i2H24S123Ag11Te.1 Agl1Te.r formation: 3.7.4.2.1 Agu*C96HsoS1 6 ~ -
Compound Index AgxNbSz AgxNbSz formation by thermal and electrochemical intercalation: 3.1 1.6.1.2 intercalate ion ordering: 3.1 1.6.1.2 AgxSaTa AgxTaSz formation by thermal and electrochemical intercalation: 3.1 1.6.1.2 intercalate ion ordering: 3.1 1.6.1.2 Ag,SzTi AgxTiSz formation by thermal and electrochemical intercalation: 3.1 1.6.1.2 intercalate ion ordering: 3.1 1.6.1.2 AlCazFeOs Ca2FeAlOs structure: 3.10.3.2.1.4 AIC104 Ag[C1041 reaction with [(CH3)2N]3PO:3.7.2.4.1 AIGeNa04 NaAlGeO4 structure: 3.10.3.3.3 AIzMg04 MgAIz04 solid state formation: 3.10.1.1.3 spinel structure: 3.10.2.3.2 A1203 "f-Ah03 defect spinel: 3.10.2.3.2 A1203 A1203 foreign atom defects: 3. 10. 1.1.2 formation of solid solutions: 3.10.1.5.5 phase formation: 3.10.3.4.2 superstructure movement: 3.10.3.4.2 AIzTe3 A12Te3 reaction with HCI: 3.8.4 Ah*C36H84ErOI 2 A13 *C36H84GdOI 2 AI~*C~~H~~HOO~Z As*AgFs As*CZH~F~NO AS*C~~H~OAUN~S~~ As*F5 AsFg03SXez (FXeOSOFOXeF) + As&formation: 3.9.3 AsFllOTeXe XeOTeF5 + A&formation: 3.9.3 AsS33[AsS3]3-
351
352
Compound Index
AuBrTez (Continued) Au*C36H30F6PzSezSb AuClSe AuClSe synthesis: 3.7.4.2.2 AuClTez AuClTez synthesis: 3.7.4.2.2 AuC14[AuCbIreaction of: 3.7.3.6 reaction to form [Au(OH)d]-: 3.7.2.7.1 reduction with dialkylsulfides: 3.7.3.3 AuCI4H HAuC14 reaction with HzS: 3.7.3.6 Au*HC14 AuH20~ Au(OH)z reaction with H2Se03: 3.7.4.4.2 Au*H4NS3 Au*H404 Au*H404Au*H I zN43+ AuITe AuITe synthesis: 3.7.4.2.2 AuITez AuITe;? synthesis: 3.7.4.2.2 AuO2 Au(qz-Oz)(matrix-isolated species) formation: 3.7.2.1.1 AuOz Au-02 matrix isolation: 3.7.2.8 AU04 Au(0z)z matrix isolation: 3.7.2.8 AuS AuS formation: 3.7.3.2 solubility: 3.7.3.2 AuS9[AuS91formation: 3.7.3.6 AuSe AuSe Au-Se system: 3.7.4.1.1 AuTez AuTe2 formation: 3.7.4.1.2 Auz*C6H1zNzSez AUZ*C~HI&'ZS Auz*C~HZIPZS+
Compound Index BF3 BF3 byproduct of reaction of B(OTeF5)3 with xenon fluorides and oxyfluorides: 3.9.3 catalyst: 3.9.2 BFls03Te3 B(OTeFd3 reaction with KrFz: 3.9.4 reaction with xenon fluorides and oxyfluorides: 3.9.3 B*H4K BH4Li LiBH4 reducing agent: 3.1 1.6.1.1 B*H4Na Bz*C~HZ~C~ZFXNIZS~ Bz *CI~ H ~ o C U Z F ~ N ~ S ~ Iz Bz*C2oHzoC~N40 BzCuFg CUPF~IZ reaction with CsH5NO: 3.7.2.4.1 B~04Rbx RbxB~04 structure: 3.10.3.2.4.4 B2*Rbx04 BZS3 BZS3 reactivity toward metal oxides: 3.8.3.6.1 Ba*C4Hx013Ti BaCi8Hdz06 Ba(K222)2+ electrointercalation: 3.1 1.6.1.7 BaFelz019 BaFelz019 coherent intergrowth of 3.10.1.5.4 structure: 3.10.3.2.2.1 BaFelai2026 BaNizFe16026 structure: 3.10.3.2.2.1 BaMnaOl6 BaMnxOl6 structure: 3.10.3.3.3 BaMo~014P4 BaMozO14P4 structure: 3.10.3.3.5.4 BaNbS3 BaNbS3 from BaCO3 and Nb02: 3.1 1.4.2 BaNbX03Tii-, BaTi 1.,Nb,O3 semiconducting oxides: 3.10.2.3.1 BaNi03 BaNi03 structures related to: 3.1 1.4.2
BaO BaO non-stoichiometric oxide: 3.10.2.1 BaO3Ti BaTiO3 insulating oxides: 3.10.2.3.1 Ba04U BaU04 rutile type structure: 3.10.3.4.3 BaO9Tb BaTi409 structure: 3.10.3.3.2 Ba014P4Tiz BaTizP40I 4 structure: 3.10.3.3.5.4 Ba014P4Vz BaVzP40 14 structure: 3.10.3.3.5.4 BaTa1-~03-r.s~ BaTa1.~03.zs~ nonstoichiometric oxide: 3.10.2.3.3 Bao.sFeSz BaosFeSz formation by ion exchange: 3.1 1.6.3 Ba1-,Lax03Ti Ba 1.,La,TiOs charge compensation: 3.10.2.3.1 Bao.63Ka.lNb14060P9
[email protected]'9060 structurehynthesis: 3.10.3.3.5.2 Baz*CzHsFe~zOzz Ba~CaCuzHgO6 HgBa2CaCuz06 structure: 3.10.3.2.1 BazCaCuzO7Tl TlBa2CaCu207 structure: 3.10.3.2.1 Ba~CaCu~08Tlz TIzBazCaCuzOx structure: 3.10.3.2.1 BazCazCu3HgOg HgBazCazCu3Os structure: 3.10.3.2.1 BazCazCu309TI TlBazCazCu309 structure: 3.10.3.2.1 BazCa2Cu301oTlz T1zBazCazCu3010 structure: 3.10.3.2.1 Ba~Ca3Cu4HgOlo HgBazCa3Cu4010 structure: 3.10.3.2.1 BazCa3Cu4011TI TIBa2Ca3Cu4011 structure: 3.10.3.2.1
353
354 BazCa3Cu012T12 TIzBazCa3Cu4012 structure: 3.10.3.2.1 BazCuOsTI TlBazCuOs structure: 3.10.3.2.1 Ba2CuO6Tl2 TlzBa2Cu06 structure: 3.10.3.2.1 BazCu3Ln07 LnBazCu307 structure: 3.10.3.2.1 BazC11306Y YBazCu306 structure: 3.10.3.2.1 BazCu~O6.4Y YBazCW06.4 structure: 3.10.3.2.1 BazCu307Y YBazCu307 structure: 3.10.3.2.1 BatFe12022Zn2 BazZnzFelz02z structure: 3.10.3.2.2.1 Ba2Fe30046 BazFezFez8046 structure: 3.10.3.2.2.1 Bat03 BazO3 phase formation: 3.10.3.4.2 Ban-lMon03n+12[Ban-iM0n03n+llm structure: 3.10.3.2.1 BaXCuLa2-,04 Laz+B axCu04 structure: 3.10.3.2.1 Ba~CozFe24041 Ba3CozFez4041 structure: 3.10.3.2.2.1 Ba4Fe3806o Ba4FezFe3606o structure: 3.10.3.2.2.1 Bi2CazCu3010Srz Bi2SrzCa~Cu3010 stncture: 3.10.3.2.1 BizCuO,jSe2 Bi2Sr2CU06 structure: 3.10.3.2.1 Biz03 Biz03 bivariant phase oxide: 3.10.2.1 Bin-~M~nOj~+iz[Bin-1MonO3n+ilm structure: 3.10.3.2.1 Br*AuSe
Compound Index Br*AuTez Br*CzH7HgNzSe Br*CzHsHg2N4Sez Br*C3H9NRuBr*CsMnOs Br*CsOsRe Br*C&Pd Br*CsH 18NRuSSiBr*CsH18CuTe2 Br*C 1oH1zFsPdS2 Br*C14HzoFsPdSz BrCuSe3 CuBrSe3 synthesis: 3.7.4.2.2 BrCuTe CuBrTe synthesis: 3.7.4.2.2 BrCuTe2 CuBrTeZ synthesis: 3.7.4.2.2 BrFs BrF5 solvent in reaction of XeFz and CF3C(OH)NHz+ As&-: 3.9.3 83Br0383Br03Beta decay: 9.3.4 Br*C30HzoF~PdSz Br*C37H301r03Pz B~*C~OH~IJF~I~~~P Brz*C&,HgIzTe Br2*C~H8HgNzSez Brz*C4HgCdOz Brz*C4H1002Zn Br2*CSHsCuNO Brz*C6H1 2 c u 0 3 Brz*CsHl6HgSez Brz*C8HzoAuN Brz*CgH18AuNSz Brz*C 1zH24Cd06 Brz*ClzHz4Hg06 Brz*C12Hz406zn Brz*C18HlsHgPSe Br~*C24H54CdPzSez Brz*Cz4Hs4HgPzSez BrzCd CdBr2 reaction with 18-C-6: 3.7.2.5.1 reaction with C H ~ ~ ( C H ~ C H Z O ) ~ C H ~ : 3.7.2.5.1 reaction with C H ~ O ( C H Z C H ~ ~ ) ~ C H ~ : 3.7.2.5.1 reaction with CH~O(CHZCHZO)~CH~: 3.7.2.5.1
Compound Index BrzCo CoBr2 reaction with 18-C-6: 3.8.2.7.1 reaction with (CH3)zSO: 3.8.2.6.1 BrzCu CuBr2 reaction with 18-C-6: 3.7.2.5.1 reaction with CsHsNO: 3.7.2.4.1 cointercalation of two cations: 3.1 1.6.4.2 BrtHg HgBn reaction with 18-C-6: 3.7.2.5.1 BrzOW WOBr2 formation from WBr6 and S02: 3.8.2.8.1 Br2W WBr2 reaction to form WOBr2: 3.8.2.8.1 BrzZn ZnBr2 reaction with 18-C-6: 3.7.2.5.1 reaction with CH30CH2CH20CH3: 3.7.2.5.1 Br3*C6Mn206B~~*C~SHSON~N~~S~O Br3Fe FeBr3 reaction with Li2S: 3.8.3.6.1 Br4*C6H14Cd203 B~~*CEHI~N~U Br4*CloH2zCd20~ B~~*CIZH~~COZO~ Br4*C 12H36C0206S6 B~~*C!~HS~AS~O~U BrqFeqS42[Fe&Br4]2synthesis of 3.8.3.6.1 BrgRe&$[Re&Brg]2synthesis of 3.8.3.6.1 Br9Re3 Re3Br9 reactivity toward S2-: 3.8.3.6.1 C CAgF303S Ag[O3SCF31 reaction with cryptand-222: 3.7.2.5.1 CAgO3 OC-AgD21 matrix isolation: 3.7.2.8 CAu02 OC-Au-0 matrix isolation: 3.7.2.8
355
CCIF3Se CF3SeC1 use in formation of Hg(SeCF3)2: 3.7.4.5.1 CClZS CSCI2 reactivity with Ti-S compounds: 3.8.3.6.3 CCl3F FCC13 solvent for Xe(OTeF5)z and Xe(OSeF5)z: 3.9.3 CC4 CC4 solvent in TiO(N03)z and ZrO(NO3)z formation: 3.8.3.8.1 CCoXNbzS2 Cox"b2S~Cl formation: 3.1 1.6.2 CCr,NbzSz Crx[NbzS2Cl formation: 3.1 1.6.2 CCuo.7NbzSz Cuo.7NbzS2C deintercalation: 3.11.6 CCuo.7NbzSz CUO.~(N~ZS~C) precursor for the preparation of Nb2S2C: 3.1 1.6.2 CCuxNb2Sz Cux"b2S~Cl formation: 3.1 1.6.2 CF403SXe FXeOS02CF3 preparation: 3.9.3 CFeO3 FeCO3 formation from Fe(C0)s: 3.8.2.1.2 CFexNb2S2 Fex"b2S2Cl formation: 3.1 1.6.2 CHF3OjS F3CS(OH)02 reaction with XeF2: 3.9.3 CH3Cu CH3Cu reaction with CH3OH: 3.7.2.2.2 reaction with n-C4H90H: 3.7.2.2.2 reaction with s - C ~ H ~ O H 3.7.2.2.2 : reaction with C - C ~ H ~ O3.7.2.2.2 H: reaction with (CH2)sCHOH: 3.7.2.2.2
1
reaction with C6HsOH: 3.7.2.2.2 CH3CuO CH30Cu
356
Compound Index
CH3CuO (Continued) formation from CH3Cu and CHsOH: 3.7.2.2.2 CH3FOXe CH3OXeF formation: 3.9.2 CH3HgNO3 CH3HgNO3 reaction with (CH3)zS: 3.7.3.3 CHLIO LiOCH3 use as a base: 3.8.3.6.3 CH3N02 CH3N02 formation of anhydrous nitrates: 3.7.2.6.1 CH3NaS NaSCH3 reaction of 3.7.3.6 CH~AUN~SI+ iAu[SC(NHz)211I+ formation: 3.7.3.3 CH4C12NiO NiC12 CH30H reaction with i-C3H70H: 3.8.2.4.1 reaction with t-CdHgOH: 3.8.2.4.1 reaction with r-C5H11OH: 3.8.2.4.1 CH~CWN~S+ CW[SC(NH~)~I~+ formation: 3.7.3.3 CH4HgO CH3HgOH use in formation of CH3SeHgOzCCH3: 3.7.4.5.1 CH4N2S SC(NH2)z complex with Hg(I1): 3.7.3.3 CH40 CH40H reaction with XeF2: 3.9.2 CH4OjS H3CS(OH)02 reaction with XeF2: 3.9.3 CMn,NbzSz Mnx[Nb2S2Cl formation: 3.11.6.2 CNbzNi,S2 Nix[Nb2S2C] formation: 3.1 1.6.2 CNbzS2 Nb2S2C formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 preparation by deintercalation: 3.1 1.6.2 CNbzS2Vx Vx"b2S2Cl
formation: 3.1 1.6.2
co2 co2
addition to Ni(PL3)3 [L=cyclohexyl, ethyl, butyl]: 3.8.2.8.1 formation of (EtC00)zZn; ( P ~ ~ P ) ~ C U ( O O C C3.7.2.6.3 H~): formation of ZnO: 3.7.2.6.1 insertion into transition metals: 3.8.3.8.2 reaction with early transition metals: 3.8.2.8.3 CSZTa2 Ta2S2C intercalation: 3.1 1.6.2 CSe2 CSe2 formation and reaction o f 3.8.4 CzAuKN2S2 K[Au(SCN)21 formation: 3.7.3.2 CzAuN2SjIAu(SCN)zIreaction with Sx2-: 3.7.3.6 C2Au04 OC-AU(CO)(O~) matrix isolation: 3.7.2.8 C~CON~S~ CO[SCN]2 reaction with cryptand-221: 3.8.2.7.1 c2cuo4 cuc204
formation of Cu: 3.7.3.1.1 C2FaHgSe Hg(SeDF3h formation: 3.7.4.6.1.1 CzF60S (CF3)2S=O reaction with XeF+, SbFs-: 3.9.2 CzFsSez (CFMez use in formation of Hg(SeCF3)2: 3.7.4.5.1 CzFsSezHg Hg(SeCF3)z formation: 3.7.4.5.1 CzF130SXe~ (CF3)2SOXeF+,SbF6formation: 3.9.2 CzHF30z F3CC(O)OH reaction with XeF2: 3.9.3 CZH4 H2C=CHz oxidation on Ag surfaces: 3.7.2.1.3 CzH4C14HgN2Se~ [(Hg(NH2)CSe)C1212
Compound Index formation: 3.7.4.6.2.7 CzH4FeO OCH2CH2Fe matrix isolation: 3.8.2.1 1 CzH4LizSz Li2[SzCzH41 as precursor to complexes: 3.8.3.6.3 CzH4NazSz Na2[S~CzH41 as precursor to complexes: 3.8.3.6.3 CZH402 CH3COOH solvent in Co(I1) acetate ozonation: 3.8.2.1.2 CzHsNO CH3C(O)NH2 protonation of: 3.9.3 CZHsNaO NaOCH2CH3 reaction to form NaZn2(0CH2CH3)5: 3.7.2.7.1 CzHdsFcjNO CH3C(OH)NH2 + reaction with XeF2: 3.9.3 CzHsBazFelzOzz Ba(CH3)2Fe12022 coherent intergrowth of 3.10.1.5.4 CzH&rtHgIzTe Me2TeI2HgBr2 formation from organochalcogenide: 3.7.4.6.2.2 CzHaCd Cd(CH3)z reaction with CH30H: 3.7.2.2.2 reaction with C2H50H: 3.7.2.2.2 reaction with i-C3H70H: 3.7.2.2.2 reaction with 1C ~ H ~ C H ( C H Z ) ~ C ( O ) C H ~3.7.2.4.2 CH~:
u
reaction with C6H5CH(CH3)CHO: 3.7.2.4.2 reaction with C6HsCH(C2H5)CHO: 3.7.2.4.2 reaction with C,jH5CH(C3H7-i)CHO: 3.1.2.4.2 reaction with CsHsOH: 3.7.2.2.2 reaction to form MeCdOO-Bu-t: 3.7.2.3.1 use in MOCVD: 3.7.4.7 CzH&dO [CH3CdOCH3]4 formation from (CH3)zCd and CH30H: 3.7.2.2.2 C~H~C~~MO~Z Mo(OCH3)2C13 formation from methanolysis of MoC15: 3.8.2.4.2
357
CzH6CO0z Co(OCH3)z formation from CoC12 and CH3OLi: 3.8.2.10.1 CzH6HgSez Hg(CHdzSe2 use in formation of CH3SeHg02CCH3: 3.7.4.5.1 CzH6HgSez Hg(SeCH3)z formation: 3.7.4.5.1 CzH6Hg20 (CH3Hgh formation from CH3HgN[Si(CH3)3]2 and Hz0: 3.7.2.2.2 CzHaiOz Ni(OCH3)z formation from NiC12 and CH30Li: 3.8.2.10.1 CzHsOS (CHd2SO solvent in metal disulfate dissolution: 3.8.2.8.3 CzH6OZn [CH3ZnOCH3]4 formation from (CH3)2Zn and CH30H: 3.7.2.2.2 CzH60ZIl [C2H5ZnOHlz formation from (C2H5)2Zn and H20: 3.7.2.2.2 CzH6OzZn Zn(OCH3)2 formation from (CH3)zZn and CH3OH at 70-80°C: 3.7.2.2.2 CzHaSO (CH3)zSO formation of crystalline solvates of Cu, Zn, Cd: 3.7.2.6.1 CZH&zSiZ[(CH~hSiSz12use as ligand: 3.8.3.6.1 CzH6Zn (CH3)zZn reaction with CH3OH: 3.7.2.2.2 reaction with C2HsOH: 3.7.2.2.2 reaction with i-QH7OH: 3.7.2.2.2 reaction with tC ~ H ~ C H ( C H ~ ) ~ C ( O ) C H 3.7.2.4.2 ZCH~:
I
I
reaction with t-CdH90H at 70°C in C6H6: 3.7.2.2.2 reaction with t-CdH90H: 3.7.2.2.2 reaction with C6H5CH(CH3)CHO: 3.7.2.4.2
358
Compound Index
CzH6Zn (Continued) reaction with C&CH(C2H5)CHO: 3.7.2.4.2 reaction with C~HSCH(C~H~-~)CHO: 3.7.2.4.2 reaction with C&OH: 3.7.2.2.2 reaction with n-Cl2H250H at 70-80": 3.7.2.2.2 use in MOCVD: 3.7.4.7 CzH7BrHgNzSe [CH3HgSeC(NH2)2]Br formation: 3.7.4.5.2 formation: 3.7.4.6.2.7 CzH7CIHgNz04Se [CH3HgSeC(NHz)2]C104 formation: 3.7.4.6.2.7 CzH7CIHgNzSe [CH3HgSeC(NHz)z]CI formation: 3.7.4.5.2 formation: 3.7.4.6.2.7 CzH7CIHg04NzSe [CH3HgSeC(NHz)zC104 formation: 3.7.4.5.2 CzH7HgN303Se [CH~H~S~C(NH~)ZINO~ formation: 3.7.4.6.2.7 CzH7Hg03NsSe [CH3HgSeC(NHz)21NO3 formation: 3.7.4.5.2 C~HsBrHgzN4Sez [Hg(NHz)zCSel2Br formation: 3.7.4.5.2 CzHsBrzHgNzSez Hg[(NHz)zCSelzBrz formation: 3.7.4.6.2.7 CzH&IHgzN4se~ [Hg(NHz)zCSel2CI formation: 3.7.4.5.2 C~H8c12HgNzSe~ Hg[(NHz)2CSe12Clz formation: 3.7.4.6.2.7 CzHsC14HgzSez [Hg(NH2)2CSe)CIzlz formation: 3.7.4.5.2 C~H14CuoN6Sez Cu(NH3)4(SeCN)2Hz0 formation: 3.7.4.5.2 CzH14HgCuN6Sez Cu(NH3)4(SeCN)2 H20 formation: 3.7.4.6.2.7 CzHziNsRUSZ+ [RWW)~(CZHSSH)P+ synthesis of 3.8.3.6.3 CzNSz S2CCn-
extrudes S to form [ C ~ S - S ~ C ~ ( C N ) ~ ] ~ - : 3.7.3.5.1 CzOzRuSesZ[Ru(Se4)dCO)zl2formation: 3.8.4 Cz04Ti (OCO)Ti(O)(CO) matrix isolation: 3.8.2.1 1.3 Cz.sHz.~+~No.~SzTa (PYH+)O.~PY )o.dTaS21 proposed composition of the pyridin intercalation compound: 3.11.6.1.6 C3BF906 B(OC02CFd3 reaction with XeF2: 3.9.3 C3BF909S3 B(OS02CF3)3 reaction with XeF2: 3.9.3 c3cTo3s63-
[Cr(SzCO)313synthesis o f 3.8.3.6.2 C3H4Cr03 Cr(OCH3h formation from CrC13 3C4HsO and CH30Li: 3.8.2.10.1 C3HsNzS SCNCHzCHzNH complex with Cd(I1): 3.7.3.3 C3H6 HzC=CHCH3 oxidation on CuzO surfaces: 3.7.2.1.3 C3H6HgOzSe CH3SeHg02CCH3 formation: 3.7.4.5.1 C3H6HgOzSe MeSeHgOzCMe formation from a selenophenol: 3.7.4.6.2.3 C3H$JzS SCNHCHzCHzNH complex with Ag(1): 3.7.3.3 C3H602 CH3CHzCOOH acidifying Cu, Ag, Hg reactions: 3.7.2.3.1 C3H7Cd i-CsH7Cd reaction with (K4Hg)OH: 3.7.2.3.1 C3H7N02S HSCHzCH(NH2)COOH reaction with IB and IIB elements: 3.7.3.5.2 C3H8 CH~CHZCH~ formation from (i-C3H7)2Hg and t-BuOH: 3.7.2.3.1
Compound Index CjHsCdO [CH3CdOCzH514 formation from (CH3)2Cd and C2H50H: 3.7.2.2.2 C3HsC12NiO NiCl2 i-C3H70H formation from [NiClZ CH30H and iC3H70H: 3.8.2.4.1 C3H802 CH~COOCHZCH~ formation of anhydrous nitrates with N204: 3.7.2.6.1 solvent in V02N02 and U02(N03)2 formation: 3.8.2.8.3 C3HsOZn [CH3ZnOCzH514 formation from (CH3)zZn and C2H50H: 3.7.2.2.2 C~H~AU (CHd3Au reaction with HSR: 3.7.3.2 C3H9BrNRu[Ru(N)(CH3)3Brlreactivity toward Me3SiS-: 3.8.3.6.1 C3H9Cr03 Cr(OCH3h formation from Cr(NO)[N(i-C3H7)2]3and CH3OH: 3.8.2.4.2 C~H~CU~S~[c~(SCH3)31formation: 3.7.3.6 C3H9HgS+ [CH3HgS(CH3)21+ formation: 3.7.3.3 C3H9NaSSi [(CH3)3SiS]Na synthesis of: 3.8.3.6.1 CjH9PS SP(CH3h complex with Cu(1): 3.7.3.3 C3HloSi4Te HTeSi(SiMe3)s formation: 3.7.4.7 C~H~~F~PRUS “-~)~R~S(CH~)~IPFZ reported: 3.8.3.3 C4C1204Rh2 RhzCldC0)4 reactivity with thiolates: 3.8.3.6.3 C4COF604 Co(OOCCF3)z formation from CoCl2 and AgOOCCF3: 3.8.2.10.1 C4CoHgN4Se4 HgCo(NCSe)4
359
formation: 3.7.4.6.2.7 c4cOO4 COZ(CO)8 reaction with CF3COCH2COCF3: 3.8.2.7.2 C4CrO4Te42[Cr(Te4)(C0)412formation: 3.8.4 C4F6HgSz [H~S~C~(CF~)ZI~ formation: 3.7.3.5.1 C4F6Mn04 Mn(OOCCF3)2 formation from MnC12 and AgOOCCF3: 3.8.2.10.1 C4FsMoSz Mo(S~CZ(CF~)Z) formation: 3.8.3.5.1 C4Fai04 Ni(OOCCF3)2 formation from NiC12 and AgOOCCF3: 3.8.2.10.1 C4F604Xe Xe(OCOCF3)2 preparation: 3.9.3 C4F&2 (CF3)2CzSz reaction with Cu, Au: 3.7.3.5.1 C4F6SzW W(S2WCF3M formation: 3.8.3.5.1 C4F1003 (CF3CO)zO solvent for reaction of XeF4 and CF3C02H: 3.9.3 C4F120sXe Xe(OCOCF3)4 claimed: 3.9.3 CdFe042[Fe(C0)412reaction of 3.8.4 CdH4AuNa04S AuS[CHCO~(CH~CO~H)]N~ Myochrysine-gold sodium thiomalate (formation): 3.7.3.6 C4H6CO04 Co(OOCCH3)2 ozonation to form Co2012C10H18: 3.8.2.1.2 C4H6Hg04 Hg(0Ach or Hg(CH3COdz reaction with S,2-: 3.7.3.6 C4H604S H02CCH(SH)CH2C02H reaction with Ag(I), Zn(II), Hg(I1): 3.7.3.5.2
360
Compound Index
C4H604Zn (CH3COO)zZn formation from EtzZn and CO2: 3.7.2.6.3 C4HsBa013Ti BaTiO(C204)2 4H20 precursor of a perovskite: 3.10.2.3.3 C4HsClCuSez CuCl(C4H8Sen) formation: 3.7.4.6.2.8 C4HsClzHgSe [Hg(C4HsSe)lClz formation: 3.7.4.5.2 formation: 3.7.4.6.2.8 C4HsCI3MoOz MoOC13(THF) reactivity toward thiolates: 3.8.3.6.3 C~H~COS~Z[CO(SZC~H~)ZI~synthesis of 3.8.3.6.3 C4HsTe Me(CH2CHCHz)Te use in MOCVD: 3.7.4.7 C4H9BrzCdOz 2CdBr2 C H ~ O ( C H Z C H ~ O ) ~ C H ~ formation: 3.7.2.5.1 C4H9CdCIzOz 2CdC12 CH~O(CHZCHZO)~CH~ formation: 3.7.2.5.1 C~H~CUO CuOC(CH3)3 oxidation by (t-Bu)zOz to form Cu(0But ) Z : 3.7.2.7.2 C4H9CuO n-CsHgOCu formation from CH3Cu and n-CdHgOH: 3.7.2.2.2 C4H9CuO s-C~H~OCU formation from CH3Cu and s-C4HgOH: 3.7.2.2.2 C4H9CuO t-QH9OCu formation from CH3Cu and t-C4H90H: 3.7.2.2.2 C4H9CuTe C4HgTeCu formation from organochalcogenide: 3.7.4.6.2.2 C4H9HgSe Hg(Set-Bu) formation: 3.7.4.5.2 C4H9Li C4H9Li reducing agent intercalation: 3.11.6.1.1
C4H9NaO NaOC4H9 use in synthesis of Mo-S compounds: 3.8.3.6.1 C4H9NbS42[NbS3(SC4H9)12as precursor to complexes: 3.8.3.6.3 CsHioBrzOzZn ZnBr;? CH30CHzCHzOCH3 formation from ZnBrz and CH3OCH2CH20CH3: 3.7.2.5.1 C4HioCd Cd(CH3CH2)z reaction to form Cd[OOEt]z: 3.7.2.1.2 C4HioCdIzOz CdIz CH30CHzCHzOCH3 formation from CdIz and CH~OCH~CH~OCHZ: 3.7.2.5.1 C4HioCdO [CH3CdOi-C3H7]4 formation from (CH3)zCd and i-C3H70H: 3.7.2.2.2 C4HioCd02Sz [Cd(SCHzCH20H)2] formation: 3.7.3.6 C4HioCd04 Cd[OO(CHzCH3)12 formation from CdEt2: 3.7.2.1.2 C4HioC1zHgOz HgC12 C H ~ O C H ~ C H Z O C H ~ formation from HgC12 and CH30CHzCHzOCH3: 3.7.2.5.1 C4HioClzNiO NiC12 t-C4HgOH formation from [NiClz. CH30H] and tC4HgOH: 3.8.2.4.1 C4HioC00z Co(OC2H5)z formation from CoC12 and CzH50Li: 3.8.2.10.1 C4Hi0FezN404Sz Fez(SCzH5)dNOh synthesis of 3.8.3.6.3 C4HioFe6Si14[F~~S~(SCZH~)ZI~as precursor to complexes: 3.8.3.6.3 C4HioHgSz Hg(SCzH5)z melting point: 3.7.3.2 C4HloHgSe Hg(SeEt)z formation: 3.7.4.6.1.1 GHioHgSez Hg(SeCzH5)z formation: 3.7.4.5.1
Compound Index C4HloLiO LiOCH(CH3)3 reaction with CuCl to form CuOBu-t: 3.7.2.7.1 C4HloNiOz Ni(OC2hh formation from NiC12 and C2HsOLi: 3.8.2.10.1 C4H100 HOWH3)3 reaction with (i-C3H7)2: 3.7.2.3.1 C4HloOZn [CH3ZnOi-C3H7]4 formation from (CH3)zZn and i-C3H70H: 3.7.2.2.2 C4HloOzZn Zn(OCzHs)z formation from (CH3)lZn and C2H50H at 70-80°C: 3.7.2.2.2 C4Hl& C4HioSH reaction with metal borohydrides: 3.8.3.6.3 C4HloZn (CWH2Wn reaction with C 0 2 to form (EtC00)2Zn: 3.7.2.6.3 CsHloZn (CzH5hZn reaction with CH3COCH2COCH3: 3.7.2.5.1 reaction with (C&)2CO: 3.7.2.4.2 reaction with H20: 3.7.2.2. use in MOCVD: 3.7.4.7 C4hAgNSe5 [(Me4N)Ag(Ses)ln formation from polychalcogenide: 3.7.4.6.2.1 C4H1zAgNTe4 [Me4NI[Ag(Te)41 formation from polychalcogenide: 3.7.4.6.2.1 C~H~ZAUPS Au(SCH3)(P(CH3)3) formation: 3.7.3.6 C~H~~CI~COOZ CoC12 2CzHsOH formation from CoC12 6H2O and C2H50H: 3.8.2.4.1 C~HIZC~ZO~SZW WO~CI~*~(CH~)ZSO formation: 3.8.6.2.3 C~H~ZCI~MOOJSZ MoOCl3*2(CH3)2SO formation: 3.8.6.2.3
C4HizC13Nb03S2 NbOC13 2(CH3)2SO formation from NbCl5 and (CH3)zSO: 3.8.2.6.3 C~H~ZCOPZS~ [Co(S2PMe2)2In geometry: 3.8.3.4.2 C4HizCuNTe4 [Me4Nl[Cu(Te4)1 formation from polychalcogenide: 3.7.4.6.2.1 CsHizMo04 Mo(OCHd4 formation from Mo[N(CH3)2]4 and CH30H: 3.8.2.4.2 C4Hiz04W [W(OCH3)414 formation from W2[N(CH3)2]6 and CH30H: 3.8.2.4.3 C4H16C13Cr04 [Cr(CH30H)4Cl2]Cl formation from CrCl3 and CH30H: 3.8.2.4.1 formation from [crCI3*3C4HgOI and CH3OH: 3.8.2.4.1 C4Hi6C1304V [V(CH3OH)4C12]CI formation from VCl3 and CH3OH: 3.8.2.4.1 C4Mo04Te42[Mo(Te4)(CO)41*formation: 3.8.4 C4NzNazSz NazSzCdCNh complex with metal salts: 3.7.3.5.2 CqNzS22[c~s-S~C~(CN)~]~reaction with Zn(II), Cd(II), Cu(II), Au(II1): 3.7.3.5.1 C4Ni04 Ni(C0)4 reaction to form Ni(N03)4: 3.8.2.8.3 C404Te3WZ+ [W(CO)4(cyclo-Te3)]2+ formation: 3.8.4 C404Te4Wz[W(Te4)(CO)412formation: 3.8.4 CsBrMnOs Mn(C0)sBr reaction with AgOOCCF3: 3.8.2.10.1 reaction with C2HsOH: 3.8.2.4.2 reaction with i-C3H70H: 3.8.2.4.2 reaction with n-C4HgOH: 3.8.2.4.2 reactivity with thiolates: 3.8.3.6.3
36 1
362
Compound Index
CsBrOsRe Re(C0)sBr reaction with AgOOCCF3: 3.8.2.10.1 reactivity with thiolates: 3.8.3.6.3 CsCIMn05 Mn(C0)sCl reactivity with thiolates: 3.8.3.6.3 CsClOsRe Re(C0)sCl reactivity with thiolates: 3.8.3.6.3 CSF12 FC(CFzhCF3 solvent for formation of Xe(OTeFs)6 and OXe(0TeFs)d: 3.9.3 CsFeO5 Fe(W5 ozonation to form FeCO3: 3.8.2.1.2 reaction with CH~COCHZCOCH~: 3.8.2.7.2 reaction with SH-: 3.8.3.6.1 reaction with Se: 3.8.4 CsHMnOsS Mn(C0)5SH synthesis of: 3.8.3.6.1 CsHOsSW[W(CO)sSHIsynthesis of: 3.8.3.6.1 CsHzOsSW W(C0)5CHzS formation: 3.8.3.2.3 CsH$X3N202 (CsHs)Cr(N0)2CI reactivity toward thiolates: 3.8.3.6.3 C5HsCIzCuNO [CUClz C ~ H S N O ] ~ formation from CuC12 and C5HsNO: 3.7.2.4.1 CsHsClzMo C5HsMoC12 reaction with NazSe5: 3.8.4 CsHsCIzW CsHsWClz reaction with NazSes: 3.8.4 CsHsC13Ti (CsHs)TiCl3 reactivity toward polysulfido anions: 3.8.3.6.2 CsH5CuBr2NO [CuBrz CSHSNOIZ formation from CuBr2 and CsHsNO: 3.7.2.4.1 CsHsCuIzNO [ C U I ~CsHsN012 * formation from CuI2 and C5H5NO: 3.7.2.4.1
CsHsMn04 Mn(OCzHs)(CO)3 formation from [MnBr(CO)s] and CzH50H: 3.8.2.4.2 CsHsMoSe4 Cd-bMo(Se)4 formation: 3.8.4 CsHsMoSe8[CsHsMo(Se4)~1formation: 3.8.4 CsHsSe4W CsHsW(Se14 formation: 3.8.4 CsHsNOzS2(CH~)ZC(S)CH(NHZ)(CO~)~reaction of 3.7.3.6 CsHllCuTe CsHllTeCu formation from organochalcogenide: 3.1.4.6.2.2 CsHu %HI2 solvent in [IrCl(OCOCOz)(PMe3)3] formation: 3.8.2.8.1 CsHizCd [CH3Cd-C-(CH3)3] formation of Cd[OOC(CH3)3]: 3.7.2.3.1 CsH12C12NiO 10H NiCIz z-C~HI formation from [NiC12CH3OH] and tCsHiiOH: 3.8.2.4.1 CsHnHgSe MeHgSet-Bu formation from organochalcogenide: 3.7.4.6.2.2 CsH120Zn CH~Z~OC-C~H~ formation from (CH3)zZn and t-C4H90H at 70°C: 3.7.2.2.2 CsHlzOZn [CH~Z~OC-C~H~]~ formation from (CH&Zn and t-C4H90H: 3.7.2.2.2 CsHieC130sW W(OCH3)2C13 3CH3OH formation from methanolysis of WC15: 3.8.2.4.2 CsIOsW[W(CO)sIIreactivity toward sulfur anions: 3.8.3.6.1 C6AgFsS AgSC6Fs in synthesis of metal thiolates: 3.8.3.6.3 C&rFSPd C6FsPdBr
Compound Index reactive intermediate: 3.8.2.1 1.2 C&I'3Mnz06[MnzBr3(CO)slreactivity with thiolates: 3.8.3.6.3 C6CrF906 Cr(OOCCF3)3 formation from crc13 and AgOOCCF3: 3.8.2.10.1 C6CrO6 Cr(CO)a reaction to form Cr(N03)6: 3.8.2.8.3 reaction with CH3COCH2COCH3and CF~COCHZCOCF~: 3.8.2.7.2 reaction with [Te4]2-: 3.8.4 reactivity toward polysulfido anions: 3.8.3.6.2 CsF5Ns NaSC6Fs reaction of 3.7.3.6 CsFsFeO6 Fe(OOCCF3)3 formation from FeCI3 and AgOOCCF3: 3.8.2.10.1 c&14
F~C(CFZ)~CF~ solvent for formation of Xe(OTeF5)4: 3.9.3 C&ezOaSz*[FezS2(C0)6I2synthesis of 3.8.3.6.1 c6Fez06Tez Fez(Tez)(CO)6 formation: 3.8.4 C&z06Te3~[Fez(Te)(Tez)(C0)61*formation: 3.8.4 C&e206Te42[Fe2(TeMC0)612formation: 3.8.4 C6HsAgSe AgSePh electrochemical formation: 3.7.4.6.1.2 cascu C6HsCu reaction with CsHsOH: 3.7.2.2.2 c6H5cuo C6HsOCu formation from CH3Cu and C6HsOH: 3.7.2.2.2 formation from C6HsCU and CsHsOH: 3.7.2.2.2 C&5CuSe CuSePh electrochemical formation: 3.7.4.6.1.2 C&5CuTe C&TeCu
363
formation from organochalcogenide: 3.7.4.6.2.2 CasFeIO Fe(CsHs)(CO)I reaction with Li2Se4: 3.8.4 C6HsKS KSCsHs reaction with metal ions: 3.7.3.2 CaHsNaSe NaSePh starting material: 3.7.4.5.2 CSHsPS32[C6H5P%I2use as ligand: 3.8.3.6.1 C6H5S[C~HSSIuse as ligand: 3.8.3.6.3 C6H6 C6H6 as solvent in Cr(Ot-Bu)4 formation: 3.8.2.5.1 solvent in Cu(OBu-t)2 formation: 3.7.2.7.2 solvent in [IrCl(OCOCO2)(PMe3)3] formation: 3.8.2.8.1 C6HsN2S C5H4NCSNH2 reaction with Cu(II), Au(II), Zn(II), Cd(I1): 3.1.3.5.2 C6HaS CsHsSH reaction with AgN03: 3.7.3.6 reaction with Cu(N03)~and amines: 3.7.3.2
reaction with Zn salt: 3.7.3.2 C6H7CIzTi (MeC5Hd)TiClz reactivity toward (Me3Si)zS: 3.8.3.6.1 CaH7Mn04 Mn(i-OC3H7)(C0)3 formation from [MnBr(CO)s] and iC3H70H: 3.8.2.4.2 C6H7N CsHsNHz solvent in [(PPh3)3RuH(OOCH)] formation: 3.8.2.8.2 C6H7N pyridine formation of Cu-0 adducts: 3.7.2.1.2 C~ioCOLaN605 LaCO(CN)6 5H20 precursor of a perovskite: 3.10.2.3.3 CsHioHg Hg(HZC=CHCH2)2 reaction with singlet 0 2 : 3.7.2.1.3
364
ComDound Index
C6H1&$4 Hg(H2C=CHCHz00)2 formation: 3.7.2.1.3 C6H1~OZN20&42[ M o ~ O ~ S~1212~CY synthesis of 3.8.3.6.3 C6HioM0zNzOsSz MO~O~(P-O)Z(CYS)~ synthesis of 3.8.3.6.3 C6HioPdS4W WS~[P~(C~HS)I~ synthesis of: 3.8.3.6.1 C6HiiA~OsS CHSAu(CHOH)3CHOCH20H Solganol-gold thioglucose(formation): 3.7.3.6 C6HllCUO (CH2)sCHOCu
U
formation from CH3Cu and (CH2)sCHOH: 3.7.2.2.2 U C6HizAg4NzSen [(Pr4N)21[Ag4(Se4)31 formation from polychalcogenide: 3.7.4.6.2.1 CsHlzAuzNzSez [(CH3)2AuNCSelz formation: 3.7.4.6.2.7 C6HizBrzCu03 [Cu( 18-C-6)][CuBr4] formation from CuBr2 and 18-C-6: 3.7.2.5.1 C6H12CIZCUO3 [CU(18-C-6)][CuC14] formation from CuCl2 and 18-C-6: 3.7.2.5.1 C6HizCW004 M o o c h (C4H802)l.S formation: 3.8.6.2.3 c6H12cU4s6z-
[CU~(SCH~CH~S)~]~formation: 3.7.3.6 C6HizMnS6~[Mn(S2CzH4)312synthesis of 3.8.3.6.3 C6H1zNzSe4Zn Zn[Me2NCSe2]2 formation: 3.7.4.5.2 C6HizNzSe4Zn Zn[MezNC(Se)Se]z formation from a dialkylselenocarbamate: 3.7.4.6.2.5 C6HizNbS6[Nb(SzCzH4)31as precursor to complexes: 3.8.3.6.3
C6H1zNizS62[Ni2(SzC2H4)312synthesis of 3.8.3.6.3 C~H~ZS~T~Z“WSZCZH~)~IZsynthesis of 3.8.3.6.3 C6H14Br4Cdz03 2CdBrz CH~O(CHZCHZO)~CH~ formation: 3.7.2.5.1 C6Hi4Cd (C3H7)zCd reaction with C3H7CdOOC4Hg: 3.7.2.3.1 C6Hi4Cd (n-C3H7)2Cd reaction with tC~H~CH(CHZ)~C(O)CH~CH~: 3.7.2.4.2 1
1
C6Hi4CdIz03 CdI2*CH~O(CHZCHZO)ZCH~ formation: 3.7.2.5.1 C6HuCdO C3H7CdOC3H7 formation from (C3H7)2Cd and C3H7CdOOC4Hg: 3.7.2.3.1 C6Hi4CdzC1403 2CdC12 CH~O(CHZCH~O)ZCH~ formation: 3.7.2.5.1 C6HisC1zHgO3 HgC12 C H ~ O ( C H ~ C H Z O ) ~ C H ~ formation: 3.7.2.5.1 c6H14COoZ Co(Oi-C3H7)2 formation from CoClz and i-C3H7OLi: 3.8.2.10.1 C6Hi4Hg (C3H7)2Hg reaction with C3H7HgOOC4Hg: 3.7.2.3.1 CaHi4Hg (i-C3H7)2Hg reaction with (K4Hg)OH: 3.7.2.3.1 C6Hi4HgO C2H7HgOC3H7 formation from (C3H7)zHg and C3H700C4Hg: 3.7.2.3.1 C6Hi4NiOz Ni(Oi-C3H7)2 formation from NiC12 and i-CsH7OLi: 3.8.2.10.1 C6Hi4NiOz Ni(On-C3H7)2 formation from NiC12 and n-QH7OLi: 3.8.2.10.1 CaHi4OzZn Zn(Oi-CsH7)z formation from (CH3)zZn and i-C3H7OH
Compound Index at 70-80°C: 3.7.2.2.2 CsH14Zn (n-GH7)zZn reaction with f C~H~CH(CH~)ZC(O)CHZCHZ: 3.7.2.4.2 I
C~H~~AUCIP (CzH5)3PAuCI reaction with Na2S: 3.7.3.2 C6H15CrO3 Cr(OCzHd3 formation from crc13 3C4H80 and C2H5OLi: 3.8.2.10.1 CaHisFe~S73[Fe3S4(SCzH5)413as precursor to complexes: 3.8.3.6.3 C6HlSO4V WOCzHs)3 formation from voc13 and CzH50Na: 3.8.2.10.1 c6H15p PEt3 ligand for MO& clusters: 3.8.3.6.1 C6HlsPTe (CzHd3PTe reaction o f 3.8.4 C6H16BLi LiBHEt3 for reduction of s8: 3.8.3.6.2 C6H16C1~03Ti TiClz(OCzH5)z CzH50H formation from Tic14 and CzH50H: 3.8.2.4.2 CaH16NzSsZn ZnS6(C6Hi6Nz) reactivity toward transition metal halides: 3.8.3.6.2 c6H16N2s6zn ZnSs(TMEDA) or Z ~ S ~ ( C ~ H ~ ~ N Z ) reaction of: 3.7.3.6 C6Hi7NS [Et3NHI[SHJ precursor to SH complexes: 3.8.3.6.1 C6HlSAU2PZS AuzS(PMe3)z reaction with HzS: 3.7.3.6 CalsBrNRuSSitRu(N)(CH3)3[SSi(CH3)311synthesis of 3.8.3.6.1 C&sCdSezSis Cd(SeSi(SiCH3)z)z formation: 3.7.4.7 CalsCdSisTez Cd(TeSi(SiCH3)z)z formation: 3.7.4.7
365
C6H18C1403S3U {UC12[OS(CH3)2161[UC161 formation from (CH3)zS.O: 3.8.2.6.1 formation from uc4: 3.8.2.6.1 C6HisCIizNaOizSbzZn [Z~(CH~N~Z)~I[S~C~~]Z reactions with 18-C-6: 3.7.2.5.1 CaHisHgSezSis Hg(SeSi(SiCH3)z)z formation: 3.7.4.7 CaHisHgSisTez Hg(TeSi(SiCH3)z)z formation: 3.7.4.7 C6HisLmbO6 Li[Nb(OCH3)6] formation from NbCl5 and CH3OLi: 3.8.2.10.1 CdtsLiOsTa Li[Ta(OCH3)6] formation from TaCl5 and CH30Li: 3.8.2.10.1 C6HisMoN3 M0AN(CHdzJ6 reaction with (CzH&,COH: 3.8.2.4.2 C6HiaNTi {Ti[N(CH3)2131 2 reaction with C&OH: 3.8.2.4.3 CsHisNzW Wz"(CH3)z16 reaction with excess CH30H and CzH50H: 3.8.2.4.3 CaHisN30P OP(N(CH3M3 solvent for intercalation reactions: 3.1 1.6.1.1 CaHiaN3W Wz"(CH3h16 reaction with excess in i-C3H70H: 3.8.2.4.3 reaction with t-C4HgOH: 3.8.2.4.2 C6Hl806W W(OCH3)6 formation from W[N(CH3)2/6 and CH3OH: 3.8.2.4.2 C6HisSSiz (Me3Si)zS synthesis of: 3.8.3.6.1 C6HzoCdNzSe4 Cd(Se2CNEtz)Z formation: 3.7.4.7 CaHaHgNSiz CH3HgN[Si(CH3)31z reaction with Hz0: 3.7.2.2.2 C6Hz4BzCuzFsNi2Ss CUZ[SC(NHZ)ZI~(BF~)Z formation: 3.7.3.3
366
Compound Index
CaMnz06SsZ[Mn2(S4)2(C0)612synthesis of 3.8.3.6.2 C,jMnzO&e42[Mn2(Se2)2(CO)612formation: 3.8.4 C,jMn20&$[Mn2(Se4)2(C0)612decomposition: 3.8.4 ~ 6 ~ 0 0 6
MO(CO)~ reaction with CH3COCH2COCH3: 3.8.2.7.2 reaction with CH3COCH2COCH3and CF3COCH2COCF3:3.8.2.7.2 reaction with [Te#-: 3.8.4
caiso62-
“i6(C0)6I2reaction with PhzTe2: 3.8.4 C606Re2Se42[Re2(Se2)2(C0)612formation: 3.8.4 C606Re2Ses2[Re2(Se4)z(C0)6I2decomposition: 3.8.4 C606W W(C016 reaction to form W(N03)6: 3.8.2.8.3 reaction with [Te4]2-: 3.8.4 reactivity toward polysulfido anions: 3.8.3.6.2 C7F3Mn07 Mn(C0)5(00CCF3) formation from Mn(C0)sBr and AgOOCCF3: 3.8.2.10.1 C7F307Re Re(C0)5(00CCF3) formation from Re(C0)sBr and AgOOCCF3: 3.8.2.10.1 C7HsCIFe02 (C5H5)Fe(C0)2CI reactivity with thiolates: 3.8.3.6.3 C7HsCIFe02 (h5-C5H5)Fe(C0)2C1 reaction with NaSZCNMe2: 3.8.3.4.2 C7HsMoOzSez[C~H5Mo(Sez)(C0)21formation: 3.8.4 C7H6NazS2 Na2S2C6H3CH3 reaction with [AuC14]-: 3.7.3.6 C7HsCdO [CH~C~OC~HSI~ formation from (CH3)2Cd and CsHsOH: 3.7.2.2.2
C7HsOZn [CH3ZnOC6H514 formation from (CH&Zn and CsH50H: 3.7.2.2.2 C7H9Mn04 Mn(n-OC4H9)(C0)3 formation from [MnBr(CO)s] and nC4H90H: 3.8.2.4.2 C7HloCIzM002 T~~-C~H~MOO(OCZH~)C~Z formation from (~pCsH5)2MoOC12and C2H50H: 3.8.2.4.2 C7HloCIzOTi ~~-C~H~T~(OCZH~)C~Z formation from (rp-C5H5)2TiC12 and C2H50H: 3.8.2.4.2 C7HioC1zOzW Tl5-CsHsWO(OC2H5)C12 formation from (qW5H5)2WOC12 and C2H5OH: 3.8.2.4.2 C7Hi0S2 C6H5-1-CH3-3,4-SH for Zn, Cd, Hg analysis: 3.7.3.5.1 C7H120zZn C2H5Zn(CH3COCH=COCH3) formation from (C2H5)2Zn and CH3COCH2COCH3: 3.7.2.5.1 C~HI~MONO~SZ MoO~(S~CN(C~H~)Z) reaction with H2S: 3.8.3.2.1 C7H16Hg0 C3H7HgOC4H9 formation from (C3H7)zHg and C3H7Hg02C4H9: 3.7.2.3.1 C7H16Hgoz i-C3H7HgOO-t-C4H9 formation from (i-C3H7)2 and r-BuOH: 3.7.2.3.1 C.rHi6HgOz C3H7HgOOC4H9 reaction with (CsH7)zHg: 3.7.2.3.1 C7Hz0SSiz [(CH3)3Si]2HCSH reaction of 3.7.3.6 C~H~~AUZP~S+ [MeS IAu[P(CH3)31121+ formation: 3.7.3.6 CgAgNqS43[AgS4C4(CN)413formation: 3.7.3.5.2 CsAuN4S43[AuS~C~(CN)~I~formation: 3.7.3.5.2 CSC0208 COZ(CO)S
Compound Index reaction to form Co2(N03)8: 3.8.2.8.3 CSCUN&~[CuS4C4(CN)413formation: 3.7.3.5.2 CsFeOsSezW2+ [WFe(COMSe2)1*+ formation: 3.8.4 CsH2MozOsSz[M0z(SH)z(C0)812synthesis of: 3.8.3.6.1 CsH5CIMo03 (Cdh)Mo(CO)3Cl reactivity with thio1ates:S 3.8.3.6.3 CsH5C103W (V-CsHs)W(C0)3C1 reaction with NaS2CNR2: 3.8.3.4.2 CsHsFe206Sz [Fe(C0)3SCH31z reaction with NaSzCNEtz: 3.8.3.4.2 CsH9C104Rh2S Rhz(SC4H9)(C1)(C0)4 synthesis of 3.8.3.6.3 CsH90Te p-EtOCsH4Te use as Te donor ligand: 3.7.4.5.2 CaHnBr4N4U UBr4 4CH3CN reaction with (CH3)3AsO: 3.8.2.6.1 CsHizM020s Moz(CH3C00)4 formation of dimer: 3.8.3.4.2 CsHitN4SaZn ZnS6(N-MeIm)z or Z ~ S ~ ( C ~ H ~ N Z ) Z formation: 3.7.3.6 CsHi4MdS6 MoO(S~CSC~H~)~ formation: 3.8.3.4.2 CsHitAg4A~2Ss2[AUZA~~(SCHZCHZS)~]~formation: 3.7.3.6 C~HI&U~CU~S~~[AUZCU~(SCHZCH~S)~]~formation: 3.7.3.6 CaH16Br2HgSe2 [(C4HsSe)zHgBrz formation from tetrahydroselenophene: 3.7.4.6.2.8 CsHi6Ch04S2W W02C12*2(CH2)4SO formation: 3.8.6.2.3 CsHi6C13M003 MoOC13 (C4H802) formation: 3.8.6.2.3 CeHlsFe2Ss2[Fez(SzCzH4)412-
367
synthesis of 3.8.3.6.3 CsH16HgI2Se2 [HgMC4HsSe)d formation: 3.7.4.5.2 CsHiaHgI2Set [(C4HsSe)zHgI2 formation from tetrahydroselenophene: 3.1.4.6.2.8 CsH16Mn2Ss2[Mn2(SzCzH4)412synthesis of: 3.8.3.6.3 ~sHi6N~OioU U02(N03)2* 2C4H80 reaction with (CF3)3CONa: 3.8.2.10.1 CsHiaSsVz2[Vz(SzCzH4)412synthesis of: 3.8.3.6.3 CsHlsBrCuTe2 BuqTezCuBr formation from organochalcogenide: 3.1.4.6.2.2 CsHiaCdI204 CdIz C H ~ O ( C H ~ C H Z O ) ~ C H ~ formation: 3.1.2.5.1 CsH~sClCuTez BunpTe2CuCl formation from organochalcogenide: 3.7.4.6.2.2 CeHieClzHg04 HgC12 CH~O(CHZCHZO)~CH~ formation: 3.7.2.5.1 CsHisHgSez Hg(Ser-Bu)z formation from a selenophenol: 3.7.4.6.2.3 CsHlsNbS4“bSz(SC4H9)zIas precursor to complexes: 3.8.3.6.3 CsHlsNiOz Ni(Ot-C4H9)2 formation from NiC12 and r-CdH90Li: 3.8.2.10.1 CsHl802 (CH3)3COOC(CHd3 formation of Cu(0Bu-r);?:3.7.2.7.2 C8Hl802 [(CH3)3CIzOz reaction to form Cr(Ot-Bu)4: 3.8.2.5.1 CsHlsOzZn Zn(Or-C4H9)2 formation from (C&)2Zn and t-C4HgOH at 70°C: 3.7.2.2.2 CsHisTe (tBu)zTe use in MOCVD: 3.7.4.7
368
Compound Index
CsHlsZn (i-C4H9)2Zn reaction with (C6H5)(CF3)CO: 3.7.2.4.2 reaction with (C6H5)(CH3)CO: 3.7.2.4.2 reaction with (C&,)(C2H5)CO: 3.7.2.4.2 reaction with (C&)(i-C3H7)CO: 3.7.2.4.2 reaction with (C6H5)(f-C4Hg)CO: 3.7.2.4.2 CsHzoAg4N4Se16 [(Et"g(Se4)14 formation from polychalcogenide: 3.7.4.6.2.1 CsHzoAuBrzN [(CzH5)4NI[AuBrzI reaction of 3.7.3.6 CsH2oCdOr Cd(OOC4Hio)z thermal explosion: 3.7.2.3.1 CsH2oCoS42[CO(SC~HS)~I*synthesis of 3.8.3.6.3 C~H2fieS42Fe(SC2H51412synthesis of 3.8.3.6.3 CeHz0Fe4Ss2[F~~S~(SC~HS)~I~as precursor to complexes: 3.8.3.6.3 CsH2a004 Mo(OCzHd4 formation from Mo[N(CH3)2]4 and C2H5OH: 3.8.2.4.2 CsHz004Ti Ti(OC2Hd4 formation from Tic14 and C2H50Na: 3.8.2.10.1 CsH2oOP U(OC2Hs)4 formation from (n3-C3H5)4U and C2H50H:
CsH24MoN4 Mo"(CH3)214 reaction with CH3OH: 3.8.2.4.2 reaction with C2HsOH: 3.8.2.4.2 reaction with i-C3H7OH: 3.8.2.4.2 reaction with K4H9CH20H: 3.8.2.4.2 reaction with r-CdHgOH: 3.8.2.4.2 CsH24N4V (V"(CH3)214 reaction with i-C3H7OH and t-C4HgOH: 3.8.2.4.2 CsHuSes [(CH3)4Nl2Ses formation 3.8.4 CsHwS% [(CH3)4Nl2Se6 formation: 3.8.4 CsH~6CdNzSe4Zn (CH3)2CdZn(Se2CNEt2)2 formation: 3.7.4.7 CsH40C14NzSTi (NEt&TiSC14 synthesis of 3.8.3.6.1 C&&ZnJ[ZnS4G(CN)413formation: 3.7.3.5.2 CsFe309Tez FedTe)z(CO)u formation: 3.8.4 C9HFejS09 [Fe3(wS)(CO)gH-Isynthesis of 3.8.3.6.1 C9HsBF305SW C5H5W(C0)30S(OBF3)CH3 formation from CpW(C0)3CH3: 3.8.2.8.2 C9HsMoO6 Mo(CO)S(OC~HE) reactivity toward SH-: 3.8.3.6.1
Compound Index CgHziCrN3 Cr"(i-CH(CH3)z)h reaction with C02: 3.8.2.8.2 C~HZIMOZN~OSS~ MOZOZ(CI-S)Z(S~)(DMF)~ synthesis o f 3.8.3.6.1 C9HziN3 (CH3hC6HizN3 ligand in Mn-S complexes: 3.8.3.6.1 CgHz3N3MnOS4 Mn(S4)(H20)[(CH3)3TACNl synthesis o f 3.8.3.6.1 CgHzsC1303V VC13 3(n-C3H70H) formation from VCI3 and n-C3H70H: 3.8.2.4.1 CioCoHio [(WsHs)zCol+ electrointercalation: 3.1 1.6.1.7 intercalation by flocculation: 3.1 1.6.1.7 CioH6CoFizOe CO(CF~COCH=COCF~)~ 2H20 formation from COz(CO)8 and CF3COCHzCOCF3: 3.8.2.7.2 CioHsFeOs (C4Hs)Fe(C0)6 reaction with [Te#-: 3.8.4 CloHsCdNSe Cd(Se-2-NCsH4)z formation: 3.7.4.6.2.9 CioHsCUF604 CU(CF~COCH=COCH~)~ formation from CuC12, NH40H and CF3COCH2COCH3: 3.7.2.5.1 CioH8F604Zn Zn(CF3COCH=COCH3)2 formation from ZnClz, NH40H and CF3COCHzCOCH3: 3.7.2.5.1 CioHsHgNSe Hg(Se-2-NCsH& formation: 3.7.4.6.2.9 CioHioClzMo (C5H5)zMoCIz reaction with [PhEI-: 3.8.4 reactivity toward polysulfido anions: 3.8.3.6.2 CloHioClzMoO (Q~-C~H~)ZMOOCIZ reaction with CzH50H: 3.8.2.4.2 CioHioClzNb (C5H5)zNbCh reaction with [PhE]-: 3.8.4 CioHioC1zOW (WY%hWOCh
reaction with CzH50H: 3.8.2.4.2 CioHioClzTi (CsHd2TiClz reaction with [PhEI-: 3.8.4 reactivity toward polysulfido anions: 3.8.3.6.2 CIoHiOCIZTi (r(s-CsHs)zTiC12 reaction with AgOOCCF3: 3.8.2.10.1 reaction with C2H50H: 3.8.2.4.2 CioHioClzV (CsHdzVC12 reaction with [PhEI-: 3.8.4 reactivity toward polysulfido anions: 3.8.3.6.2 CioHioChV (V-C~H~)ZVC~Z reaction with Na dithiocarbamates Na xanthates: 3.8.3.4.2 CioHioChW (CsHd2WCh reaction with [PhEI-: 3.8.4 reactivity toward polysulfido anions: 3.8.3.6.2 CioHioCIzZr (V-CsHs)zZrCh reaction with AgOOCCF3 and AgOOCC3F7: 3.8.2.10.1 CioHioClzZr (C~H~)ZZ~~Z reaction with [PhEI-: 3.8.4 CloHioCr (t15-CsHs)zCr reaction with r-C4HgOH: 3.8.2.4.2 CioHioHfSs (C5H5)zHfSs synthesis of 3.8.3.6.2 CioHioM& (CsHs)zMoS4 synthesis of: 3.8.3.6.2 CioHioNz06SezZn [Zn(PySeSePy)(N03)z1 formation: 3.7.4.6.2.9 CioHioNi (CsHdzNi reactivity with thiols: 3.8.3.6.3 CioHioS4W (CsHdzWS4 synthesis o f 3.8.3.6.2 CioHioSsTi (CsHs)zTiSs synthesis of 3.8.3.6.2 CioHioSsV (C5Hs)zVSs synthesis of: 3.8.3.6.2
369
370
Compound Index
CioHioSsZr (CsH5)zZrSs synthesis of 3.8.3.6.2 CioHioV (c5H512v reactions with organosulfur compounds: 3.8.3.6.3 CioHiiFeNOzSz (~~-C~HS)F~(CO)~S~CNM~~ formation: 3.8.3.4.2 CloH1zBrFsPdS~ [(CH~)~P~(B~)(C~F~)Z synthesis from metal atoms: 3.8.3.7.2 CIOHIZMOS (C~H~)~MO(SH)Z synthesis of 3.8.3.6.1 CioHizM0zS4 [C~H~MO(S)SHI~ formation: 3.8.3.2.1 CloHlzSTi (C~H~)ZT~(SH)Z synthesis of 3.8.3.6.1 CioHizSW (C~H~)ZW(W~ synthesis of: 3.8.3.6.1 CioHizSzTi (TI~-CSH~)ZT~(SH)~ formation: 3.8.3.2.3 CioHizZr (WCsHshZrHz reaction with (CH3)zCO: 3.8.2.6.2 C~OHI~BF~M~OZS
CioHi4M006 M00dC5H~Oz)z reactivity towards thiols: 3.8.3.6.3 CioH14NiS4 Ni(SacSac)z formation: 3.8.3.5.1 reaction with Ni(PEt3)CIz: 3.8.3.5.1 CioHi4S4Zn
Zn(CH3CSCHCSCH3)2Zn(SacSac)2
formation: 3.7.3.5.1 CioHisCIzORe [CdCH3)51ReOCh reactivity toward polysulfido anions: 3.8.3.6.2 CloH1sC1zReS3 [CdCH3)51ReS3C12 synthesis of 3.8.3.6.2 CioHrsCI4Re [CdCH3)51ReC14 reactivity toward polysulfido anions: 3.8.3.6.2 CloHisC14Ta [CdCH3)5lTaC14 reaction with Li2S: 3.8.3.6.1 CioHisC14W [C5(CH3)51WCh reactivity with thiolates: 3.8.3.6.3 CioHisOReS4 [CdCH3)51ReO(S4) synthesis of: 3.8.3.6.2 CioHisReS7 [Cs(CH3)slRe(S3)(S4) [(~~-C~H~)M~(CO)ZS(CH~)~IBF~ synthesis of 3.8.3.6.2 reported: 3.8.3.3 CioHisSzWCioHi4CW004 { [CdCH3)1WS31Mo(CH~COCH=COCH~)~CI~ synthesis of 3.8.3.6.3 formation from MOC14 and CloH1~S3TazCH3COCH2COCH3: 3.8.2.7.1 { [CdCH3)51TaS312C10H14C1~04Ti synthesis o f 3.8.3.6.1 Ti(CH3COCH=COCH3)2CI2 ~ 1 ~ 1 8 ~ ~ 2 ~ 1 2 formation from Tic14 and C~Z(~ZCCH~)~(OH)Z(NO~CCH~) CH3COCH2COCH3: 3.8.2.7.1 formation from cobalt(I1) acetate ozonation: 3.8.2.1.2 CioHi4CIz04V V(CH3COCH=COCH3)2C12 CioHzoAuzNzSz formation from VC14 and [(CzHdzAuSCNIz CH3COCH2COCH3: 3.8.2.7.1 characterized: 3.7.3.2 CioHi4C1z04W CioHzoC14C~zOs W(CH3COCH=COCH3)2C12 [Cu( 15-C-5)][CUC14] formation from WC14 and formation from CuC12 and 15-C-5: 3.7.2.5.1 CH3COCH2COCH3: 3.8.2.7.1 CroHzoCrNzOS4 CioH14C1304Pa C~(S~CN(C~H~)Z)(OS~CN(C~H~)~ Pa(CH3COCH=COCH3)2C13 structure: 3.8.3.4.2 formation from PaCl5 and CioHzoCuNzSe4 CH3COCH2COCH3: 3.8.2.7.1 Cu[EtzNC(Se)Se]2
371
Compound Index formation from a dialkylselenocarbamate: 3.7.4.6.2.5 CioHzoNzSe4Zn Zn(Et2NC(Se)Se]z formation from a dialkylselenocarbamate: 3.7.4.6.2.5 CioH20N3ReS4 ReN(SzCNEt2)z formation: 3.8.3.4.2 structure: 3.8.3.4.2 CioHzoOzU (V-C~H~)ZU(OCZH~)~ formation from (q3-C3H5)4U and CzH50H: 3.8.2.4.2 C10HzzBr4Cd20s 2CdBrz C H ~ O ( C H Z C H ~ O ) ~ C H ~ formation: 3.7.2.5.1 CioH2zCdI~Os CdIz C H ~ O ( C H ~ C H Z O ) ~ C H ~ formation: 3.7.2.5.1 CioHzzCdzC140s 2CdC12 C H ~ O ( C H ~ C H Z O ) ~ C H ~ formation: 3.7.2.5.1 CioHzzC12HgOs HgC12 C H ~ O ( C H ~ C H Z O ) ~ C H ~ formation: 3.7.2.5.1 CioH24C13N4Nb03 NbOCI3 2(CH3)2NCON(CH3)2 formation: 3.8.2.6.3 CioHzsNaZn20s “aZnz(OCHzCH3)51 formation from ZnC12 and NaOEt: 3.7.2.7.1 CioHmN4Ta t-C4H9N=Ta[N(CH3)2]3 reaction with (C6H5)2CO: 3.8.2.6.2 CioHzaSSi3 [(CH3hSil3CSH reaction of: 3.7.3.6 CI~H~AU~P~S+~ [M@S(Au[WH3)313I+ formation: 3.7.3.6 CioMn2010 Mnz(CO)10 reaction of 3.8.4 reacrjon to form Mn(N03)lo: 3.8.2.8.3 reactivity toward polysulfido anions: 3.8.3.6.2 CIO~CO,HIO~S~S~ [CoCpz+lxSnSz lithium uptake: 3.11.6.1.7 CiiHnFe [(rl-CsHs)(rl-C6H6)Fel+ electrointercalation: 3.1 1.6.1.7
intercalation by ion exchange: 3.1 1.6.1.7 CiiHlzFsNiO (I , ~ - C ~ H ~ ~ ) N ~ O C ( C F ~ ) Z
i
formation with (1,5-CsH12)2Ni:3.8.2.6.1 formation with (CF3)zCO: 3.8.2.6.1 CllH1~02Zn C6H5Zn(CH3COCH=COCH3) formation from (C6H5)zZn and CH3COCH2COCH3: 3.7.2.5.1 CiiHisMdSa{ [CS(CH~)~IMO(S~)(S~CO))synthesis of 3.8.3.6.2 CiiHi6CdO CH~C~OCH(CH~)CH(CH~)C~HS formation from (CH3)zCd and C6H5CH(CH3)CHO:3.7.2.4.2 CiiH160Zn CH3ZnOCH(CH3)CH(CH3)C6H5 formation from (CH3)zZn and CsH5CH(CH3)CHO: 3.7.2.4.2 CllH22ClNiPSz NiCI(SacSac)PEts formation: 3.8.3.5.1 C11H~~ClizN07Sb2Zn { Zn[CH30(CHzCH20)4CH3]* CH3NOzI [SbCklz formation: 3.7.2.5.1 CllH27CIIr04P3 [I~l(OCOCOz)(P(CH3)31 formation from [IrCI(CsH14)(PMe3)3: 3.8.2.8.1 CizCrHiz [(Tl-C6H6)2CrIf electrointercalation: 3.1 1.6.1.7 intercalation by ion exchange: 3.1 1.6.1.7 C12Fe3012Te2[Te(Fe(C0)41312formation: 3.8.4 CizH4CldW m-CIC6H4HgOC~C15 formation from (m-CIC6H4)zHgand C6C150H: 3.7.2.2.2 CizH4CWgO p-ClCrjH4HgOC6C15 formation from @-CIcf,H4)zHg and C6C150H: 3.7.2.2.2 CizH4C16HgO (O-C1C6H4HgOC6C15 formation from (o-CIC6H4)zHg and C6C150H: 3.7.2.2.2 CizH4M~Oi2S4 Mn4(CO)dSH)4 synthesis of 3.8.3.6.1
372
Compound Index
reaction to form [(CpzTi)z(CO3)Iz: 3.8.2.8.3 CizHioOzZr [(C~H~)ZZ~(CO)ZI reaction to form [(C5H5)2Zr0]3: 3.8.2.8.3 Ci2HiOS (C6H5)zS formation: 3.7.3.6 CizHiOSz (C6Hd2S2 use in synthesis of PhS complexes: 3.8.3.6.3 CizHioSez (C6H5)zSez reaction of 3.8.4 CizHloTez (C6HdzTez formation: 3.8.4 CizHioZn (C6HshZn reaction with r-C4H90H at 70°C in C6H6: 3.7.2.2.2
reaction with (CsH5)zCO: 3.7.2.4.2 reaction with CH3COCH2COCH3: 3.7.2.5.1 CizHizCr Cr(C6H6)2 oxidation to form Cr(Or-Bu)4: 3.8.2.5.1 CizHizN~ (CsH5NHh catalyst in (EtC00)zZn formation: 3.7.2.6.3 CizHi4CIzTi (CH3C5H&TiC12 reaction with [Se5]2-: 3.8.4 CizHi4Se5Ti (CH~C~H~)ZT~(S~~) formation and reaction with phosphine: 3.8.4 CizH15F30Zn i-C4HgZnOCH(CF3)C6H5 formation from (i-ChHg)zZn and (C&)(CF3)CO: 3.7.2.4.2 CizHi5M002SzI~ ~ s ~ ~ ~ ~ synthesis of 3.8.3.6.2 CizHi6C0NzSs CO(SZCC~H~NHZ)(S~CC~H~NHZ) reported in literature: 3.8.3.4.2 CizHi6MO (C~H~)ZMO(CH~)Z reaction with Se: 3.8.4 CizHi6MoSez[(C~H~)ZMO(S~CH~)ZIformation: 3.8.4 CizHi60zZr (~~~-C~H~)ZZ~(OCH~)Z formation: 3.8.2.1.3 CizHiaSzTi (C~H~)ZT~(SCH~)Z as precursor to complexes: 3.8.3.6.3 CizHi6SezW[(C~H~)ZW(S~CH~)ZIformation: 3.8.4 CizHi6W (C~H~)ZW(CH~)Z reaction with Se: 3.8.4 CizH16Zr (rl5-C5H5)zZr(CH3)2 reaction with 0 2 : 3.8.2.1.3 CizHisCd0 CH3CdOCH(CH3)CH(C2H5)C6H5 formation from (CH3)zCd and C&CH(CzH5): 3.7.2.4.2 CizHisC1izC~N6Sbz [C~(CH~(N)~I[S~C~~~Z reaction with C4H@: 3.7.2.4.1
~
~
Compound Index C12HisC11zN6SbzZn [Zn(CH3CN)al[SbC1612 reaction with C4HsO: 3.7.2.4.1 Ci2HieFi20sPzPd
373
CizHz4BrsCO206 [Co(18-C-6)][CoBr4] formation from CoBr2 and 18-C-6: 3.8.2.7.1 CizH24CdC1~06 [(CH~~)~PI~P~OC(CF~)Z~C(CF~)Z CdC12. (18-C-6) formation from CdC12 and 18-C-6: formation from (CF3)zCO: 3.8.3.6.1 3.7.2.5.1 formation from Pd[P(OCH3)3]4: 3.8.2.6.1 CizHzsCdIzOa CnHisOZn CdI2 ( 18-C-6) CH3ZnOCH(CH3)CH(C2Hs)CsH5 formation from CdIz and 18-C-6: 3.7.2.5.1 formation from (CH3)zZn and C6H5CH(C2H5)CHO: 3.7.2.4.2 CizHz4CltHgO6 HgC12 (18-C-6) CizHisOZn formation from HgC12 and 18-C-6: i-CdHgZnOCH(CH3)CsHs 3.7.2.5.1 formation from (i-C4Hg)zZn and (C&5)(CH3)CO: 3.7.2.4.2 CizH24CbCr03 crc13*3C4H& CizHis04RhzS~ reaction with (r-C4Hg)2CHOLi: 3.8.2.10.1 R~Z(SC~H~)Z(CO~ reaction with CH30H: 3.8.2.4.1 synthesis of: 3.8.3.6.3 reaction with CH3OLi, n-C4HgOLi and tCi2HzoAuPS C4H90Li: 3.8.2.10.1 (CZH~~PAUSC~H~ formation: 3.7.3.2 reaction with C2H50H: 3.8.2.4.1 reaction with i-C3H70H: 3.8.2.4.1 CI~HZOAUZN~N~ZO&~~reaction with nQH90H: 3.8.2.4.1 CI~H~OAU~N~N~~O&P formation: 3.7.3.6 reaction with n-C6H130H: 3.8.2.4.1 CizHz4C1306U Ci2HzoM0~04Ss UC13( 18-C-6) M~~SZCOCZH~)~ formation: 3.8.3.4.2 formation from UCl3 (C~HXO), and 18-C6: 3.8.2.7.1 CizHzoU (WC3H514U CizHz4C14COz06 reaction with C2HsOH at R T 3.8.2.4.2 [CO(18-C-6)][C0C14] reaction with C2HsOH at 30°C: 3.8.2.4.2 formation from CoC12 and 18-C-6: reaction with i-C3H70H at RT 3.8.2.4.2 3.8.2.7.1 reaction with i-C3H70H at 30 "C: C1~Huc14Ni~O6 3.8.2.4.2 [Ni( 18-C-6)][NiC4] formation from NiC12 and 18-C-6: reaction with t-CdH90H at RT 3.8.2.4.2 3.8.2.7.1 reaction with f-C4H90H at 30°C: 3.8.2.4.2 Ci2HziNS C12H24C11206Sb~Zn Et3NH(SC6H5) [Zn( I 8-C-6)][SbC16]2 formation: 3.7.2.5.1 as PhS- source: 3.8.3.6.3 CizHuHgIz06 CizHuAg9Siz3HgI2*(1 8-C-6) [A~~(SCH~CHZS)~I~formation from HgI2 and 18-C-6: 3.7.2.5.1 formation: 3.7.3.6 C1~HuBrzCd06 CizH240Cd CH~C~OC(CH~)(CHZ)ZCH(C~H~-~)CH~CH~ I CdBr2 (18-C-6) formation from CdBr2 and 18-C-6: 3.7.2.5.1 formation: 3.7.2.4.2 CizHuBrzHgO6 CizHz40Zn HgBr2 ( 18-C-6) (CH~)Z~OC(CH~)(CHZ)ZCH(C~H~-~)CH~CH formation from HgBr2 and 18-C-6: 3.7.2.5.1 formation: 3.7.2.4.2 CnH24Brz06Zn CizHz402U ZnBr2 ( 18-C-6) (h3-C3H5)2U(i-OC3H7)2 formation from ZnBr2 and 18-C-6: formation from (h3-C3H5)4U and C3H70H: 3.7.2.5.1 3.8.2.4.2
u
374
Compound Index
Compound Index
375
formation from Ni(C104)2: 3.8.2.6.1 CI~H~SC~~N~OI~S~ {Ni[OS(CH3)2161[c10412 formation from Ni(C104)~:3.8.2.6.1 formation from (CH3)zSO: 3.8.2.6.1 CizH36C12014S6Zn Zn[OS(CH3)216][c10412 formation from Zn(C104)2 and (CH3)zSO: 3.7.2.4.1 Ci2H36CbFeOi8S6 (Fe[OS(CH3)216l(C104)3 formation from Fe(C104)3: 3.8.2.6.1 formation from (CH3)2SO: 3.8.2.6.1 CIZH~~C~~N~N~O~PZ NbOCI3 2{ [(CH~)ZN]~PO] formation: 3.8.2.6.3 C I ~ H ~ ~ C I ~ N ~ O ~ P ~ T ~ TaOC13 2{ [(CH~)ZN]~PO] formation: 3.8.2.6.3 CizH36C14C0206S6 CO[OS(CH3)216}[cOc141 formation from (CH3)zSO: 3.8.2.6.1 formation from CoC12: 3.8.2.6.1 C]2H&14Ni206S6 I Ni[OS(CH3)216I "iC41 formation from NiC12: 3.8.2.6.1 CizH36C1406SaTh {ThCl3[Os(CH3)2lslC1 formation from (CH3)zSO: 3.8.2.6.1 formation from ThC14: 3.8.2.6.1 CizH3sC0NzSb Co{"Si(CH3)312 l z reaction with (t-C4Hg)2CHOH:3.8.2.4.2 C ~ ~ H M C ~ N ~ S ~ Cr{"Si(CH3)31zh reaction with (t-C4H9)2CHOH:3.8.2.4.2 C12H36FeNzSb FeI N[Si(CHddz 12 reaction with thiols: 3.8.3.6.3 ClzHxMnNzSk Mn 1"Si(CH3h12 h reaction with (t-C4Hg)2CHOH:3.8.2.4.2 reaction with thiols: 3.8.3.6.3 CizH36N6W W"(CH3)z16 reaction with CHz=CHCHzOH: 3.8.2.4.2 reaction with CH3OH: 3.8.2.4.2 reaction with CzH50H: 3.8.2.4.2 reaction with i-C3H7OH: 3.8.2.4.2 reaction with n-C3H70H: 3.8.2.4.2 reaction with t-C4H90H in refluxing C6H.5: 3.8.2.4.2 CizH360izP4Pd Pd[P(OCH3)314 reaction with (CF3)zCO: 3.8.2.6.1
376
Compound Index
Compound Index CO2 insertion into Ni-C to give [Ni(bipy)COs]: 3.8.2.8.2 Ci4H18M003 [CS(CH~)SIMO(CO)~CH~ reactivity toward polysulfido anions: 3.8.3.6.2 C14HisN2Ni (C2Hs)zNi-Bipy reaction with C&isOH: 3.8.2.4.2 C14Hi8N2NiO CzHsNi(0CzHs) Bipy formation from (C2H5)2Ni Bipy and CsHsOH: 3.8.2.4.2 Ci4H2oAgNOs AgN03 benzo-15-C-5 formation from AgNOi and benzo-15-C-5: 3.7.2.5.1 C14HzoBrFsPdSz (CsFs)Pd(Br)[s(CzHs)zl2 synthesis from Pd atoms: 3.8.3.7.2 C14HzoCeN3014 Ce[NO3]3(benzo-15-C-5) formation from Ce(N03)3 6H2O and benzo-15-C-5: 3.8.2.7.1 C14HzoFezOzSz [(~~-C~H~)F~(CO)SC~HSIZ formation: 3.8.3.2.3 C14HzoFezS4 (C~HS)~F~~(SCZHS)ZSZ synthesis of 3.8.3.6.2 C14H2oFezS4 1
-
[(rl5-CsHs)Fe(Sz)(SCzHs)z
formation: 3.8.3.2.3 C14HzoLaN3014 La[NO3]3(benzo-15-C-5) formation from La(N03)3 6HzO and benzo- 15-C-5: 3.8.2.7.1 C14HzoN3NdOi4 Nd[N03]3(benzo-15-C-5) formation from Nd(N03)3 6H2O and benzo-15-C-5: 3.8.2.7.1 C14HzoN3014Pr Pr[N03]3(benzo- 15-C-5) formation from Pr(N03)3 6HzO and benzo-15-C-5: 3.8.2.7.1 C14HzoN3014Sm Sm[NO3]3(benzo-15-C-5) formation from Sm(N03)3 6H2O and benzo-15-C-5: 3.8.7.2.1 C14HzoNizSz Niz(C5Hs)z(SCzHs)z synthesis of 3.8.3.6.3 C14HzzHgTe Hg(TeAr)z (Ar=2,4,6-Me3CsHz) formation: 3.7.4.6.1.1
377
C14HzzOZn ~-C~HYZ~OCH(C~H~-~)C~HS formation from (X4Hy)zZn and ( C ~ H S ) ( C ~ H ~ - ~3.7.2.4.2 )CO: C14Hz40zS4Zn Zn(0Et-Sacsac)? structure: 3.7.3.5.1 Ci4H28MONz0S6 MoO(S~)(SZCN(C~H~)Z)Z formation: 3.8.3.2.1 CI~HZ~MO~NZS~ MozS~(S~CN(C~H~)Z)~ formation: 3.8.3.2.1 Ci4Hz802U (~~~-C~HS)~U(~-OC~HY)Z formation from (h3-C3H5)4U and tC4HgOH: 3.8.2.4.2 CisH3CrF1806 Cr(CF3COCH=COCF3)3 formation from Cr(C0)6 and CF3COCH2COCF3: 3.8.2.7.2 CisH3Fi8M006 Mo(CF3COCH=COCF3)3 formation from Mo(CO)6 and CF~COCHZCOCF~: 3.8.2.7.2 C15HiiCIN3Pt+ [PtCl(terpy)l+ reactivity with thiolates: 3.8.3.6.3 CisHiiN3S4V Werpy )(S2)2 synthesis of 3.8.3.6.2 ClsHizFsFeO6 Fe(CF3COCH=COCH3)3 formation from FeC13 and CF3COCH2COCH3in presence of CH3COONa: 3.7.8.2.1 CisHi60Zn CzHsZnOCH(C6Hs)2 formation from (CZH5)zZn and (C6Hs)zCO: 3.7.2.4.2 C15H17NOZn CzHsZnOCH2N(CsHs)z formation from C ~ H ~ Z ~ N ( C and ~H~)Z HCHO: 3.7.2.4.2 CisHz1ClO6Zr Zr(CH3COCH=COCH3)3Cl formation from ZrC14 and CH3COCH2COCH3: 3.8.2.7.1 Ci5HziCrO6 Cr(CH3COCH=COCH3)3 formation from Cr(C0)6 and CH~COCHZCOCH~: 3.8.2.7.2 CisHziFeO6 Fe(CH3COCH=COCH3)3 formation from Fe(C0)5 and CH~COCHZCOCH~: 3.8.2.7.2
378
Compound Index
CisHziFeS6 Fe(SacSac)3 formation: 3.8.3.5.1 CisHziMoOs Mo(CH3COCH=COCH3)3 formation from Mo(CO)~and CH3COCH2COCH3: 3.8.2.7.2 CisHz40Zn i-C4HsZnOCH(C4H9-r)C6H5 formation from (i-C4H9)2Zn and (C6Hs)(C4H9-l)CO:3.7.2.4.2 CisHz4S 2,4,6-(i-C3H7)3CrjH~SH reaction of 3.7.3.6 CisHzsMONOs
[E~~NI[(~~-C~H~)MO(CO)~I
reaction with 0 2 : 3.8.2.1.3 CISH~~N~N~~S~Z[Ni3S(SC4H9)s(CN)312as precursor to complexes: 3.8.3.6.3 C~SH~OCON~S~ Co(S2CNEt2)3 formation: 3.8.3.4.2 CisH.mN3S6 M(SzCN(C2H5)2)3, M = lanthanide formation: 3.8.3.4.2 CisH3oNsR~zSio+ Rw[SzCN(CH3)z15+ formation: 3.8.3.4.1 ClsH30SSi3
[(CH~)~S~IZ[(CH~)ZC~HSS~ICSH
reaction o f 3.7.3.6 Ci~H3sCILi~O6Re Li[ReO(Oi-C3H7)5]LiCl formation from ReOC14 and i-C3H7OLi: 3.8.2.10.1 CisH3sNbOs Nb(Oi-C3H7)5 formation from Nb[N(C2H5)2]4 and iC3H7OH: 3.8.2.4.3 CisH4sA~sChC0013 ( C O [ O A S ( C H ~I )[CQIz ~I~ formation from (CH3)3AsO: 3.8.2.6.1 formation from co(C104)2: 3.8.2.6.1 C~SH~SASSCIZN~O~~ {Ni[OAs(CH3)315I [C1041z formation from (CH3)3AsO: 3.8.2.6.1 formation from Ni(C104)2: 3.8.2.6.1 C~SH~SC~ZCOOI~PS (C0[0P(CH3)315I [C10412 formation from (CH3)3PO: 3.8.2.6.1 formation from Co(c104)2: 3.8.2.6.1 CisH45CIzNiOi3Ps {Ni[OP(CH3)3lsI [C10412 formation from (CH3)3PO: 3.8.2.6.1 formation from Ni(C104)2: 3.8.2.6.1
Compound Index
379
C16H3sOzTi (tritox)Ti(CH3)2(0CH3) formation: 3.8.2.1.3 C16H3s03Ti (tritox)Ti(CH3)(0CH3)2 formation: 3.8.2.1.3 Ci6H3s04Ti (tritox)Ti(OCH3)3 formation: 3.8.2.1.3 c16H3so4u U(Ot-C4H9)4 formation from (h3-C3H5)4U and tC4HgOH: 3.8.2.4.2 c16H3604v V(Ot-C4H9)4 formation from V[N(CH3)2]4 and tC4HgOH: 3.8.2.4.2 Ci6H3sOsRe ReO(Ot-C4H9)4 formation from ReOCL4 and r-C4HgOLi: 3.8.2.10.1 C16H3sOSW WO(Ot-C4H9)4 formation from W[N(CH3)2]6 and tC4H90H in refuxing C6H6: 3.8.2.4.2 c16H3sRhZP208sZ R~z(SC~H~)Z(CO)Z{ P[O(CH3)13)z formation: 3.7.2.4.2 synthesis of 3.8.3.6.3 CidI3zOZn C~~H~OBZCWF~N~S~ (~-C~H~Z~OC(C~H~-~)(CH~)~CH(C~H~-~)CH*CHZ CUZ((CH~)ZNCHZCH~SSCH~CH~N I I (CH3)z)(BF4)2 formation: 3.7.2.4.2 formation: 3.7.3.3 Ci6H3sC11~08Sb2Zn C16H40C~304V [V(S-C~H~OH)~CI~]CI { Z ~ [ C H ~ O ( C H Z C H ~ O ) I~[SbCkh CH~I~ formation: 3.7.2.5.1 formation from Vc13 and s-CdH90H: 3.8.2.4.1 C16H3sCrO4 Cr[O-C(CH3)314 Ci6H4oN4Nb formation from Cr(C6H6)z and (t-Bu)zO~: Nb"(CzW214 3.8.2.5.1 reaction with i-C3H70H: 3.8.2.4.3 reaction with r-C4H90H: 3.8.2.4.3 Ci6H3sMONOz M~~[OC(CZH~)~I~[N(CH~)~IZ Ci6H4oN4Ti formation: 3.8.2.4.2 Ti[N(C2Hs)z14 reaction with thiols: 3.8.3.6.3 C16H3sM004 M0(0t-C4H9)4 Ci6H48C~NzS4 formation from Mo[N(CH3)2]4 and t[(CZH~)~NIZC~(SZCCSH~)Z C4H90H: 3.8.2.4.2 formation: 3.7.3.4.2 CI~HMMOS~ C16H48NzS4Zn Mo(SC4H9)4 [(CZHS)~NIZZ~(S~CCSH~)~ synthesis of 3.8.3.6.3 formation: 3.7.3.4.2 Cid3sNbSsC17H1sMoSez [NbS(SC4H9)41(CsHs)Mo(SeC6Hsh as precursor to complexes: 3.8.3.6.3 formation: 3.8.4 C16HxOTi C17H1sNbSez (tritox)Ti(CH3)3 (CsHs)Nb(SeCd-k)z reaction with 0 2 : 3.8.2.1.3 formation: 3.8.4
380
Compound Index
C17H150zTi [CioHi I T ~ C ~ H ~ C O orOCp2TiC6H4COO ] formation from [Cp~TiPhz]:3.8.2.8.2 C17HisSe2Ti (CsHs)Ti(SeCsHs)z formation: 3.8.4 C17HlsSe2V (CsHs)V(SeCsHs)z formation: 3.8.4 C17HlsSe2W (CsHs)W(SeC6Hs)z formation: 3.8.4 C17H3zLnN301a Ln[NO3]g(benzo-l5-C-5). 3H202 Me2CO (Ln=Sm-Lu) formation from Ln(NO3)3 6H2O and benzo-15-C-5: 3.8.2.7.1 C17H33NiPS (hXsHs)Ni(P(C4H9)3SH formation: 3.8.3.2.3 C17H41CIIrP3 [I~CI(CXH~~)(P(CH~)~)~I formation of [IrCl(OCOCO2)(PMe3)3]: 3.8.2.8.1 Cl&r60]8Te$[C~~(T~Z)~(C~)IXI~formation: 3.8.4 C1sFe6H45P3Sa (Fe&(PEt3)312+ Intercalation by flocculation: 3.1 1.6.1.7 CiaH3LaNz06 La(K222)2+ electrointercalation: 3.1 1.6.2.7 C1aH1oF1404Zr (~~~-CSHS)ZZ~(OOCC~F~)Z formation from (~pCsH5)zZrC12and AgOOCCF3: 3.8.2.10.1 CiaHi4NzOzSV V(S)(C~~HI~NZOZ) synthesis of 3.8.3.6.1 CiaHi4N203V V(O)(CixHi4NzOz) reactivity toward (Me3Si)zS: 3.8.3.6.1 CiaHi5AuCIP AuCl(PPh3) reaction with dithietes: 3.7.3.5.1 CiaHiSAuCIPS (C~HS)~PSAUC~ formation: 3.7.3.3 ClaHl5AuClPSe AuCl Ph3PSe formation: 3.7.4.6.2.6 ClsHlsBrzHgPSe HgBrzPh3PSe formation: 3.7.4.6.2.6
ClsH15ChHgPSe HgClzPh3PSe formation: 3.7.4.6.2.6 CisHi5CuIP CuI(PPH3) reaction with dithietes: 3.7.3.5.1 CiaH15C~S32[Cu(SPh)$- or [CU(SC6H5)3]2formation: 3.7.3.6 CisHi5HgIzPSe HgI2Ph3PSe formation: 3.7.4.6.2.6 CiaHisHgI2PSe [HgClz(PPh3PSe)lz formation: 3.7.4.6.2.6 Ci&sIZPSeZn ZnPh3PSeIz formation by reaction with triphenylphosphine chalcogenides: 3.7.4.6.2.6 CiaHiB~3C~3Sa2[Au~CU~(SCH~CH~S)~]~formation: 3.7.3.6 CiaHzoAgBF402 [A~@-CH~C~H~COCH~)Z~[BF~] formation from AgBF4 and p CH3C6H4COCH3: 3.7.2.4.1 ClaHzzCdTe2 Cd(Te-2,4,6-MesCsH2)2 formation from a tellurophenol: 3.7.4.6.2.3 CiaH22Te2Zn Zn(Te-2,4,6-Me3CsH2)2 formation from a tellurophenol: 3.7.4.6.2.3 C18H23NOZn CZH~Z~OCH(~-C~H~)N(C~H~)Z formation from CzH5ZnN(C6H5)2: 3.1.2.4.2 C1aH26FezN2S2f+
[(C~H~)ZF~Z(SE~)Z(CH~CN)Z~~+
reactivity toward polysulfido anions: 3.8.3.6.2 CiaHzaCrzNzOzSz (C~H~)ZC~Z(SC~H~)Z(NO)Z synthesis of 3.8.3.6.3 CIIJH~IJC~ZS~ (C~H~)ZC~Z(SC~H~)ZS synthesis of 3.8.3.6.3 CiaHm0aW W(OCH2CH=CH2)6 formation from W[N(CH3)2]6 and CHz=CHCH20H: 3.8.2.4.2 C1aH3SAgF3N209S [Ag(cryptand-222)][03SCF3]
Compound Index formation: 3.1.2.5.1 CisH36Bflz06 (check for rest of entry under BaC1sH36NzO6) C 1~H3sC130zi fi [Pr( 12-C-4)(15-C-5)I[C10413 formation from Pr(C104)3, 12-C-4 and 15C-5: 3.8.2.7.1 CisH~sC~Niz04S7 [CU(SCNHCH~CH~NH)~](SO~) formation: 3.7.3.3 C~~HMN~N~S~ Ni(S2CN(n-Bu)2)2 reaction with ZnC12: 3.8.3.4.1 C 18H~NzSe4Zn Zn(Bu2NC(Se)Se]2 formation from a dialkylselenocarbamate: 3.7.4.6.2.5 CisH38C00z CO[OCW~-C~H~)ZI~ formation from Co{N[Si(CH3)3]2]2 and (tC4H9)zCHOH: 3.8.2.4.2 Ci8H38CrOz Cr[OCH(r-C4H9)212 formation from Cr(N[Si(CH3)3]2]2 and (tC4H9)2CHOH: 3.8.2.4.2 ClaH38MnOz Mn[OCH(t-C4H9)212 formation from Mn{N[Si(CH3)312]2and (tC4Hg)zCHOH: 3.8.2.4.2 C18H38N8025Sm [Sm(cryptand-222)N03][Sm(N03)5H20] formation: 3.8.2.7.1 ClsH4zC13Cr03 cC13 3(n-C6H13OH) formation from [CrC13 3C4HsO) and nC ~ H I ~ O 3.8.2.4.1 H: ClsH42CrN40 Cr(NO)[N(i-C3H7)213 reaction with CHjOH: 3.8.2.4.2 Cld4206W W(On-C#7)6 formation from W[N(CH3)2]6 and nC3H70H: 3.8.2.4.2 Ci8H4206W W(Oi-C3H7)6 formation from W[N(CH3)2]6 and iC3H70H: 3.8.2.4.2 C18H45NiP3 NiIP(CH2CH3)313 formation of weak dihapto(C,O-): 3.8.2.8.1 Ci8H54ASar406U W[OAS(CH3)316lBr4 formation from (CH3)3AsO: 3.8.2.6.1 formation from UBr404CH3CN: 3.8.2.6.1
ClsHg CdGezSezSiz Cd[SeGe(SiMe3)3]2 formation from a silylchalcogenide: 3.1.4.6.2.4 ClsH54CdGezSizTez Cd[TeGe(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 C18H54CdSe~Si4 Cd[SeSi(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 CleHs4CdSkTe2 Cd[TeSi(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 CisH54C14NpO6Ps {NPC~[OP(CH~)~I~IC~~ formation from (CH3)3PO: 3.8.2.6.1 formation from NpC14: 3.8.2.6.1 C18H54C140d’d’a {PaCI[OP(CH3)3]6lcl3 formation from PaC14: 3.8.2.6.1 c1sHssCl4Od‘d’u {PuCI[OP(CH3)316lCb formation from (CH3hPO: 3.8.2.6.1 formation from cS2[PUcl6]: 3.8.2.6.1 Ci8H54C1406P6Th {ThCI[OP(CH3)316)C1 formation from (CH3)3PO: 3.8.2.6.1 formation from ThC4: 3.8.2.6.1 Ci8H54C1406P6U (UCI[OP(CH3)316ICh formation from UCl4: 3.8.2.6.1 formation from (CH3)3PO: 3.8.2.6.1 C18Hs4Ge~HgSezSiz Hg[SeGe(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 ClsH54GezHgSizTez Hg[TeGe(SiMe3)3]2 formation from a silylchalcogenide: 3.1.4.6.2.4 Cl8H&ezSezSizZn Zn[SeGe(SiMe3)3]z formation from a silylchalcogenide: 3.7.4.6.2.4 ClsH54Ge2SizTezZn Zn[TeGe(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 C18H54HgSezSi.1 Hg[SeSi(SiMe3)3]2 formation from a silylchalcogenide: 3 .l A.6.2.4
381
382
Compound Index
CisHs4HgSi4Tez Hg[TeSi(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 Cis&&ezSi4Zn Zn[SeSi(SiMe3)3]2 formation from a silylchalcogenide: 3.1.4.6.2.4 ClsHssSbTezZn Zn[TeSi(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 C18H54SisTe~Zn Zn[TeSi(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 c18M060isTes2[MOdTe2)4(CO)1x12formation: 3.8.4 c18Ol8Te8W6Z[w6(TQh(Co) 1xi2formation: 3.8.4 CisHsFinNi (rl6-C7Hx)Ni(CsFh synthesis from Ni atoms: 3.8.2.1 1.2 Ci9HsNa CloHgNa reducing agent, intercalation: 3.1 1.6.1.1 C19HisNiPSz (SCS)Ni[P(C6H5)31 synthesis from active Ni powder: 3.8.3.7.2 C19H19AuCINzPSe [Ph3PAuSeC(NH2)2]Cl formation: 3.7.4.6.2.7 Ci9Hz4FaOPt
(1 ,~-C~HI~)P~OC(CF~)~CH(CH~)~CH=CH(CH~)~CH I
formation: 3.8.2.6.2 Ci9HzsNbOs Nb(0Et)~ precursor to Nb-S clusters: 3.8.3.6.1 CisHzsOsTa Ta(0Et)s precursor to Ta-S clusters: 3.8.3.6.1 CzoCr4OzoTezz[Cr4(Te2)(COh012formation: 3.8.4 CznFesOznTeio2[FexTex(Te2)(C0)2012formation: 3.8.4 CznH4Fz4HfOs Hf(CF3COCH=COCF3)4 formation from HfC14 and CF3COCH2COCF3: 3.8.2.7.1 CznH4Fz40sZr Zr(CF3COCH=COCF3)4
I
Compound Index C20Hz4ChHg06 HgC12 dibenzo-18-C-6 formation from HgC12 and dibenzo-18-C6: 3.7.2.5.1 CzoHz4C13Ln018 Ln[ClO4]3(dibenzo-18-C-6) (Ln=La-Nd, Sm, Eu and Dy) formation from Ln(C104)3 and dibenzo- 18C-6: 3.8.2.7.1 CzoHz4LnN3015 Ln[N03]3(db-18-C-6) formation from Ln(N03)3 6H2O and dibenzo- 18-C-6: 3.8.2.7.1 CzoHz6C13Er019 Er[ClO4]3(dibenzo-18-C-6) H20 formation from Er(C104)3 and dibenzo- 18C-6: 3.9.2.7.1 C~oHz6C13019Yb Yb(ClO4)3(dibenzo-l8-C-6)H20 formation from Yb(C104)3 and dibenzo- 18C-6: 3.8.2.7.1 CzoHzsChRuz [(CioH I 4P~C1212 reaction with S2-: 3.8.3.6.1 CzoHzsHfOs Hf(CH3COCH=COCH3)4 formation from HfC14 and CH3COCH2COCH3in presence of C5HloNH: 3.8.7.2.1 C2oHz808Th Th(CH3COCH=COCH3)4 formation from ThC14 and CH30CH2COCH3 in presence of C5HloNH: 3.8.7.2.1 C2oHzsOsZr Zr(CH3COCH=COCH3)4 formation from ZrC14 and CH3COCH2COCH3in presence of CsHloNH: 3.8.2.7.1 CZOHNCI~I~Z I [Cs(CH3)sIIrChh reaction with S2-: 3.8.3.6.1 CzoH3oC14Rhz {[CS(CH~)SIR~C~Z~ reaction with SZ-: 3.8.3.6.1 CZOH~OC~~RU~ [CS(CH~)SIZRWC~~ reactivity with thiolates: 3.8.3.6.3 CzoH~oCozSes [Cs(CH3)sIzCoz(Se)(Se4) formation: 3.8.4 CzoHsoOsV [ I I J - ~ ~ - C ~ C Hl V~ ()0S) O l ~~ formation: 3.8.2.1.3 CzoH3oRhzSes [Cs(CH3)sIzRhz(se)(se4)
383
formation: 3.8.4 CZOHMS~T~ [Cs(CH3)512TiS3 synthesis of 3.8.3.6.2 C~OHNV {V-CS(CH~)S hv reaction with 0 2 : 3.8.2.1.3 CZOH~~COZN~O~S~ [Co(cryptand-22I)][Co(SCN)4] formation from Co(SCN)2 and cryptand221: 3.8.2.7.1 CZOHMAUO~PS C2oH34Au09P.S Auranofin(formation): 3.7.3.6 CtOH36C14C0206 [CO(S~C-~)][COCI~] formation from CoC12 and scd-6: 3.8.2.7.1 CzoH3sLaN301s La[NO3]3(scd-6) formation from La(NO3)3 6H2O and sdc6: 3.8.2.7.1 CzoH39C13LnN3018 [Ln(cryptand-222)C104][C104]2CH3CN (LnLa-Nd, Sm and Eu) formation: 3.8.2.7.1 CzoH40C13022PI. [Pr( 15-C-5)2][Cl04]3 formation from Pr(C104)3 and 15-C-5: 3.8.2.7.1 CzoHsoCu4N4Ss [C~S2CN(CzHs)z14 example of cluster compound: 3.7.3.4.1 CZOH~OMON~S~ Mo[SzCN(C2Wz14 formation: 3.8.3.4.1 CZOH~OMO~N~OZS~Z M~z(SZ~)~(SZCNE~)~ known species: 3.8.3.4.2 CzoH44M004 Mo(O~-CH~C~H~)~ formation from Mo[N(CH3)2]4 and tC4H9CH20H: 3.8.2.4.2 CzoH4sNb05 Nb[Ot-C4H9]s formation from Nb[N(CzH5)2]4 and tC4H90H: 3.8.2.4.3 CzoH4sNisS6[N~sS(SC~H~)SIas precursor to complexes: 3.8.3.6.3 C20H48018Zr Zr(CH3COCH=COCH3)4 10Hz0 formation from zEI4 and CH3COCH2COCH3 in H20: 3.8.2.7.1 CzoHsoCo4SioZ[Co4(SC2Hs)iol2synthesis of 3.8.3.6.3
384
Compound Index
C2oHsoFe4S102[Fe4(SC2Hs)loPsynthesis of 3.8.3.6.3 CzoH54CdSezSiz Cd(SeC(SiMe3)3]2 formation from a silylchalcogenide: 3.1.4.6.2.4 CzoHs4CdSizTez Cd[TeC(SiMe3)3]2 formation from a silylchalcogenide: 3.1.4.6.2.4 CzoHs4HgSe2Siz Hg(SeC(SiMe3hlz formation from a silylchalcogenide: 3.1A6.2.4 CzoHs4HgSi2Tez Hg[TeC(SiMe3)3lz formation from a silylchalcogenide: 3.1.4.6.2.4 C2oHs401d'4Rh& Rh2(SC4H9)2{P[O(CH3)131 4 synthesis of 3.8.3.6.3 CzoH54SezSi2Zn Zn(SeC(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4 CzoHs4Si2TezZn Zn[TeC(SiMe3)3]2 formation from a silylchalcogenide: 3.7.4.6.2.4
CZIHISCOS CO(S~CC~HS)~ formation: 3.8.3.4.2 CZIH~IF~S~ Fe(SCHzC6Hd3 synthesis o f 3.8.3.6.2 C21H23Nz03SiV V(OSiMe3)(CisH14Nz02) formation of 3.8.3.6.1 C~IHJOCUN~O~S1,7-(CH3)4-2,8(CH3)2-12-azacrown-4CUS(C6H4-2-CO2) formation: 3.7.3.6 CZIH~ICIMOZO~ [IV-CS(CH~)S IMoIz(~~-C~)(~~-CO~)(~-O) formation: 3.8.2.1.3 C~IH~~CON~O~ 2-octylCo(dmgh)2py reaction with 0 2 : 3.8.2.1.3 CziH36CON506 2-octylOOCo(dmgh)2py formation: 3.8.2.1.3 C~iH36CU303S6 [Cu(OEt-SacSac)]3 formation: 3.7.3.5.1
Compound Index
385
386
Compound Index C27HsCr03 [C~(CH~C~H~-O-N(CH~)Z)~I reaction with COz: 3.8.2.8.2 C27H430zTa { 2,6-(i-Pr)zCsH30 hTadCH93 reaction with 0 2 : 3.8.2.1.3 C~~HS~CIN~N~S~ Ni(S2CN(n-Bu)2)3Cl formation: 3.8.3.4.1 CZ~HS~L~ZN~OZ~ [La(cryptand-222)(NO3)213[La(N03)61 formation: 3.8.2.7.1 Cz7H63NaOsZrz Na[Zrz(Oi-C3H7)9] formation from ZrC14 and i-C3H7ONa: 3.8.2.10.1 CzsHzoNiS4 Ni(S2C2Phd2 formation: 3.8.3.5.1 C28H2aCO [(CsHsCH2)4CO] reaction with COz to form [ ( P ~ C H ~ C O O ) ~ ( P ~ C H ~: ) Z C O ] 3.8.2.8.2 CzaHzaNi [(CsHsCH2)4Nil reaction with C02 to form [(PhCH2COO)2(PhCH2)2Ni]: 3.8.2.8.2 CzsH28Rh [(CsH5CH2)4Rhl reaction with COz to form [(PhCH2COO)2(PhCH2)2Rh]: 3.8.2.8.2 CzaHzaTi [(CsH5CHzhTil reaction to form [(PhCH2C00)2(PhCH2)2Ti]: 3.8.2.8.2 C2sH2aZr [(CsH5CH2)4Zrl reaction to form [(PhCH~C00)2(PhCH2)2Zrl:3.8.2.8.2 C2aH28ZP Zr(CHnPh)4 reaction with thiols: 3.8.3.6.3 CzsH3oAsAuN4Se4 [Ph4As][Au(SeCN)4] formation: 3.7.4.6.2.7 CzaHdr2Sz Irz(SC6Hd2(COD)2 synthesis o f 3.8.3.6.3 CzaH~RhzS2 R~~(SC~H~)Z(COD)Z synthesis of 3.8.3.6.3
Compound Index CZ~H~OC~~L~OZZ
[Ln(dibenzo-30-C-l0)][C104]3 (Ln=La-Nd, Sm and Eu)
formation from Ln(C104)3 and dibenzo-30C-10: 3.8.2.7.1 Cz8H4zAuPSi3Te Ph3PAu[TeC(SiMe3)3] formation from a silylchalcogenide: 3.7.4.6.2.4 Cz8HmHfOz (tritox)zHf(CH3)2 reaction with 0 2 : 3.8.2.1.3 CzsHmHf04 (trit0~)2Hf(OCH3)2 formation: 3.8.2.1.3 Cz8Hm02Ti (tritox)~Ti(CH3)2 reaction with 0 2 : 3.8.2.1.3 CzaHmOzZr (tritox)2Zr(CH3)2 reaction with 0 2 : 3.8.2.1.3 CzsHm04Ti (tritox)zTi(OCH3)2 formation: 3.8.2.1.3 CzaHm04Zr (tritox)zZr(OCH3)2 formation: 3.8.2.1.3 C3oFeH3oN6 [Fe(2,2’-dipyridine)3]2+
electrointercalation: 3.1 1.6.1.7 intercalation by ion exchange: 3.1 1.6.1.7 C@zoBrFsPdSz (CsFs)Pd(Br)[s(CsHs)z]z synthesis from Pd atoms: 3.8.3.7.2 c3oH2sp~ [P(C6H5)41[SC6Hd reaction with Zn(N03)~:3.7.3.6 CWHZ~CIF~I~O~PZ [CH~P(C~H~)~]ZI:C~(CO)O OC(CF3)zO I
387
388
Compound Index
C~ZHUNZSQZ~ [NMe412[Zn(SePh)41 formation from a silylchalcogenide: 3.7.4.6.2.4 C~ZHUP~P~ZSZ ~2s~[p(cH3h(c6H~)14 synthesis of: 3.8.3.6.1 C3zHm03Zr (tritox)2Zr(CH3){OC(CH3)2CH=CH2) reaction with 02: 3.8.2.1.3 C~ZH~CIIZCUOSS~Z [Cu(C4HsO)6l[SbC1612 2C4HsO formation from [Cu(CHsCN)6](sbC16)2 and C4H80: 3.7.2.4.1 C32Hdf03 (tritox)zHf(CH3){OC(CH3)2CH=CH2] reaction with 02: 3.8.2.1.3 C32Hdf05
n
(tritox)2Hf(OCH3){ OC(CH3)2CHCH20) formation: 3.8.2.1.3 C3zH6~0sZr
n
(tritox)zZr(OCH3){OC(CH3)2CHCH20] formation: 3.8.2.1.3 C3zHsoCd100i&i64+ [Cdio(SCHzCHz0H)i614+ formation: 3.7.3.6 C~zHsoSsZns [CH3ZnSC(CH3)2ls structure: 3.7.3.2 C~~HZ~.SCUPI.SS~ CuSePh 1.5Ph3P electrochemical formation: 3.7.4.6.1.2 CMH~~SOVZ (CsHs)zVz(SPh)4 synthesis of 3.8.3.6.3 C3sFeHz4N6 [Fe(phenanthroline)3]2+ electrointercalation: 3.1 1.6.1.7 C~~H~~ASZCI~N~O~ NBOCL3 ~ ( C ~ H ~ ) ~ A S O formation: 3.8.2.6.3 C36H30AuFd'zS bSez [(Ph3PSe)Au(SePPh3)][SbF6] formation: 3.7.4.6.2.6 C36H30AuFd'zSezSb [(Ph3PSe)zAul[SbF61 formation: 3.7.4.6.2.6 C&~~CIZM~O~PZ M002C12 2(C6H5)3PO formation: 3.8.6.2.3 C36H30CIzNPzRe ReNCI(PPh3)2 reaction with NaS2CNEt2: 3.8.3.4.2
C3sH30CIZPZPt PtCh[PC6H5)312 reactivity with thiolates: 3.8.3.6.3 C36H30CIzPzSezHgz [HgClzPh3PSe]z formation: 3.7.4.5.2 C~~H~~CI~MOO~PZ 2(C6H5)3PO formation: 3.8.6.2.3 CxiH&l3Nb03Pz NbOC13 2(C6H5)3PO formation: 3.8.2.6.3 Cd30C130PzRe ReOC13(PPh3)2 reaction with NaS2CNR2: 3.8.3.4.2 c36H30c1403Pus3 {PUC12[OS(C6H5)2161 [pUc161 formation from PuC14: 3.8.2.6.1 C36H30C1403S3U UC12[OS(C6H5)2]61[uc161 formation from (C&)2SO: 3.8.2.6.1 formation from UC4: 3.8.2.6.1 c36H30cO&z-
[Co2(SC6H5)6I2synthesis of 3.8.3.6.3 C36H30CU4S6Z[CU4(SPh)6]2- Or [CU4(SC6H5)6]2formation: 3.7.3.6 Ca30FezS62[Fe2(SC6H5)6I2synthesis of 3.8.3.6.3 C3SHmN03RhS [R~(NO)SO~(P(C~HS)~)~~ formation from [RhNO(PPh3)3]: 3.8.2.8.1 C36H30Nz04PzPt [pt(P(CsHd3 12WXN03) formation from Pt[(PPh3)zC2H4]: 3.8.2.8.3 C3sH3002PZPt [(C6H5)3PhPtO 0
1
reaction with (CF3)zCO: 3.8.2.6.2 reaction with CH3CHO: 3.8.2.6.2 reaction with (CH3)2CO: 3.8.2.6.2 reaction with CH3COCH2CI: 3.8.2.6.2 reaction with C2H5CHO: 3.8.2.6.2 C3SH3006W W(OC6H5)6 formation from wc16 and C6H50H at 180200°C: 3.8.2.4.2 C36H&6znZ2[Zn2(SC6H5)6I2formation: 3.7.3.6 C36H32PZPts Pt[P(C6Hs)312H(SH) formation: 3.8.3.2.3
389
Compound Index Cd44FN4Ti Ti(C36H44N4)F reactivity toward polysulfido anions: 3.8.3.6.2 Cd4FzN4Ti Ti(C36HdWF2 reactivity toward polysulfido anions: 3.8.3.6.2 C&uN4S2Ti T~(C~~HMN~)(S~ synthesis of: 3.8.3.6.2 C36H47N40zTa
t-C4HgN=Ta[OC(C6H5)2N(CH3)2]2
"(CHd21 formation: 3.8.2.6.2 formation: 3.9.2.6.2 C36HssCdSez Cd(Se-2,4,6-t-Bu3C6H2)2 formation from a selenophenol: 3.7.4.6.2.3 CdssSe2Zn Zn(Se-2,4,6-t-Bu?C6H2)2 formation from a selenophenol: 3.7.4.6.2.3 Cd69CeO6 Ce(00Cn-Cl lH23)3 formation from CeCl3 and nCllH23COONa: 3.8.2.10.1 Cd69LaO6 La(OOCn-C11H23)3 formation from Lac13 and nC1 lH23COONa: 3.8.2.10.1 C36H72N6Se4Zn [(~-C~HY)~NI~[Z~(NCS~)~ formation by reaction with selenocyanate ligand: 3.7.4.6.2.7 C3aHaiNiP3 Ni[P(CH2CH2CH2CH3)3]3 formation of weak dihapto(C,O-): 3.8.2.8.1 C36Ha43Er012 Er[Al(Oi-C3H7)4]3 formation: 3.8.2.10.1 C36HuA13GdOi2 Gd[AI(Oi-C3H7)4]3 formation: 3.8.2.10.1 C36Ha4A13H0012 Ho[Al(Oi-C3H7)4]3 formation: 3.8.2.10.1 c36H90c0#&8+
[Co6S8(PEt3)61+ synthesis of 3.8.3.6.1 C36HwFe86Saz+ [Fe6S8(PEt3)612 synthesis of 3.8.3.6.1 Cd9oNi9P6S92+ [N~YSY(PE~~)~I~ synthesis of 3.8.3.6.1 +
+
C36HioaCdzSii6Te4 {Cd[TeSi(SiMe3)3]2)2 formation from a silylchalcogenide: 3.7.4.6.2.4 C36Hi08CI3CrNi80iaP6 { CrI OP"(CH3)213 161[c10413 formation from Cr(C104)3: 3.8.2.6.1 C36HioaCbFeNi8018P6 {FeIOl"N(CH3)21316}[c10413 formation from Fe(C104)3: 3.8.2.6.1 CdioaHgzSi16Tes {Hg[TeSi(SiMe3)31212 formation from a silylchalcogenide: 3.7.4.6.2.4 C36HiosSiisTe4Znz {Zn[TeSi(SiMe3)3]2}2 formation from a silylchalcogenide: 3.7.4.6.2.4 C37H~As~ClIr03 0 [(C~HS)~AS]~I~CI(CO)O
u
reaction with (CF3)2CO: 3.8.2.6.2 C37H~BrIr03P2 [(C6HshPl2IrBr(CO)O 0
u
reaction with (CF3)2CO: 3.8.2.6.2 C37HmCIIrN20& [ W C18H15)2(CO)Cl(NO3)(NO2)1-3 formation from [Ir(PPh3)zCoCI]: 3.8.2.8.3 C37HmCIIrOP2 IrCI(CO)(PPh3)2 reactivity with thiolates: 3.8.3.6.3 C37H3oCIIr03P2 [ ( C ~ H ~ ) ~ P I Z ~ ~ (0C O ) O
u
reaction with (CF3)2CO: 3.8.2.6.2 C37H30CIIrP2 [I~{P(C~H~)~IZ(CO)CII oxidation to form
[I~(PP~~)~(CO)C~(NO~)(NOZ)]-~:
3.8.2.8.3 C37HmIIr03P2 [(C6Hd?PIzIrI(C0)0 0
u
reaction with (CF3)zCO: 3.8.2.6.2 C37HmIrP2OCI [Ir(CO)C1(P(CsHs)21 formation of dioxygen adducts: 3.8.2.1.2 C37HmOPzPtS (Ph?P)2PtS2CO formation: 3.8.3.4.2 C37H3iF3PzPt [(P~~P)~P~(SZCF)IHF~ formation: 3.8.3.4.3
390
Compound index
Compound Index
391
392
Compound Index
394
Compound Index
Compound Index formation: 3.7.3.6 Ci~1Hi40Cdi7S3~2[%Cdi7(SC6Hs)z8l2formation: 3.7.3.6 Ci68H174CU~P&6~[CU5(p-SBUt)6]1formation: 3.7.3.2 Czi6HiaoCd3zSso Cd32S14(SC6Hsh6 formation: 3.7.3.6 C~~~H~~SCUSP~~S~Z[CU~(JJZ-SPH)~I*formation: 3.7.3.2 Ca*BazCu2HgO6 Ca*Ba2Cuz07Tl Ca*Ba2CuzOsTIz CaCr204 B-CaCrzO4 structure: 3.10.3.3.3 CaCuZLaO&r LaSrCaCuzOs structure: 3.10.3.2.1 CaFeOsx CaFe03-, nonstoichiometric oxide: 3.10.2.3.3 CaFezO4 CaFe204 structure: 3.10.3.3.3 CaLnzO4 CaLn204 structure: 3.10.3.3.3 CaMnOr, CaMn)3-, nonstoichiometric oxide: 3.10.2.3.3 CaO CaO non-stoichiometric oxide: 3.10.2.1 CaO4Scz [(CH~)~NI~[C~IOS~(SC~H~)I~] CaSczO4 structure: 3.10.3.3.3 formation: 3.7.3.6 Ca04Tiz CIIZHIZ~N~SZOZ~~O CaTi204 [(CH~)~NI~[Z~IOS~)(SC~HS)I~I chemical twinning in: 3.10.1.3.3 formation: 3.7.3.6 structure: 3.10.3.3.3 CizoHis4CusSs Ca04Vz [C~(SC~HZ(~-C~H~)~)I~ CaV204 formation: 3.7.3.6 structure: 3.10.3.3.3 C~~ZHJJOCWOPZZ CaO4Ybz Cu70Se3s(PEt3)22 CaYb204 formation from a silylchalcogenide: structure: 3.10.3.3.3 3.7.4.6.2.4 Cao.~+~CszNb60z4 CIUH~Z~CU~OPIZS~~~ C%.~+~cS~Nb6024 CusoSe I dPPr3‘)12 structure/synthesis: 3.10.3.3.5.2 formation from a silylchalcogenide: Cao.sFeHzYOySz 3.7.4.6.2.4 (A2+)0,sFeS2.,H20 (M=Ca, Sr) Ci6shsAgiS3Si9 formation by ion exchange: 3.1 1.6.3 IAgSC[Si(C6Hshh 13
formation: 3.7.3.2 C96H7zFezNsO (p-O)[(rneso-tetratolylporphyrin)Fe]z formation: 3.8.2.1.3 CdsoAgTeiz tPh4PMAgzTe121 formation from polychalcogenide: 3.7.4.6.2.1 C%Ha0AgizSi6~[Agi2(SC6Hs)1d4formation: 3.7.3.6 C%HeoCdsS17~[SCds(SC6Hs)16I2formation: 3.7.3.6 C%HmCdiOS16Te44[Te4Cdlo(SPh)1614formation from a tellurophenol: 3.7.4.6.2.3 C%HsoCdloSezo4[Se4Cdlo(SePh)1614formation from a selenophenol: 3.7.4.6.2.3 C%H8OCIS16ZnIl [Zn8Cl(SC6H5)16] formation: 3.7.3.6 C%HsoCuTeiz tPh4P14[CuzTe1~1 formation from polychalcogenide: 3.7.4.6.2.1 C~O~HZSZCUZ~P~ZS~~S Cu~gSels(PPr3i)lz formation from a silylchalcogenide: 3.7.4.6.2.4 Ci08HzszCud’12Seis Cu3oSels(PPr3i)lz formation from a silylchalcogenide: 3.7.4.6.2.4 CiizHiz8CdioN4S~o
395
396
Compound Index
Cao.ssCuOzSro.~s Sro.1sCao.ssCu02 structure: 3.10.3.2.1 Ca2*AlFeOs Caz*Ba2Cu3HgOs Ca2*Ba2Cu30gT1 Ca2*Ba2Cu301oT12 Caz*Bi2Cu301oSrz CazCoFeOs CalCoFeOs structure: 3.10.3.2.1.4 Ca2Cu03 Ca2Cu03 structure: 3.10.3.2.1 CazFezOs Ca2Fe205 structure: 3.10.3.2.1.4 structurehynthesis: 3.10.3.3.5.2 Ca~Nb207 Ca2Nb207 coherent intergrowth: 3.10.1.4.1 CazNbs015Tl Ca2TlNbsOls structure: 3.10.3.3.1 Ca3*Ba2Cu4HgOlo Ca3*Ba2Cu401IT] Ca3*BazCu4012T12 Ca4Fe5013Y Ca4YFe5013 structure: 3.10.3.2.1.4 CasFe4On CasFepOn structure: 3.10.3.2.1.4 Ca7NaNbsO17 NaCa7NbsOI 7 coherent intergrowth: 3.10.1.4.1 Caz4NaNbzsOs7 NaCaz4Nb25087 coherent intergrowth: 3.10.1.4.1 C~~-IMO~O~~+IZ[Can-~M~n03n+ll structure: 3.10.3.2.1 CaXCuLaz-,04 Laz-,Ca,CuO4 structure: 3.10.3.2.1 Cd Cd active metal powder: 3.7.2.8 reaction with 0 2 : 3.7.2.1.1 reaction with steam at dull red heat: 3.7.2.2.1 Cd*Br2 CdCIz CdCl2 reaction with CH30(CH2CH20)2CH3: 3.7.2.5.1
reaction with C H ~ O ( C H ~ C H Z O ) ~ C H ~ : 3.7.2.5.1 reaction with CH30(CH2CH20)4CH3: 3.7.2.5.1 reaction with dibenzo-18-C-6: 3.7.2.5.1 reaction with 18-C-6: 3.7.2.5.1 CdClzOs Cd[C1041z reaction with (CH3)zSO: 3.7.2.4.1 CdIz CdI2 formation from chemical mass transport: 3.11.3.2 reaction with CH~OCHZCH~OCH~: 3.7.2.5.1 reaction with 18-C-6: 3.7.2.5.1 reaction with CH3O(CH2CH20)2CH3: 3.7.2.5.1 reaction with CH3O(CH2CH20)3CH3: 3.7.2.5.1 reaction with C H ~ O ( C H ~ C H Z O ) ~ C H ~ : 3.7.2.5.1 CdO CdO formation: 3.7.2.1.1 formation from Cd and steam at dull red heat: 3.7.2.2.1 non-stoichiometric oxide: 3.10.2.1 CdPSj CdPS3 intercalation by ion exchange of host metal atoms: 3.1 1.6.2 CdS CdS crystal growth: 3.1 1.3.2 exchange reaction: 3.7.4.2.1 formation: 3.7.3.1.1 formation: 3.7.3.2 formation: 3.7.3.6 nanoparticle synthesis: 3.1 1.5.1 stoichiometric adjustment: 3.1 1.3.1 CdSz CdS2 formation: 3.7.3.1.1 CdSs CdSs formation: 3.7.3.2 CdSe CdSe equilibrium: 3.7.4.2.1 formation: 3.7.4.1.1 formation: 3.7.4.3.1 formation: 3.7.4.4.1 CdTe CdTe
Compoui7d Index
397
Cdz*C6H14Br403 Cdz*C6Hi4C1403 Cd~*CloHz~Br405 Cdz*CioHzzC140s Cdz*C36HiosSi16Te4 Cdz*C38H7zNsSe6 CdzMosSes CdnMO6Se8 formation by electrointercalation: 3.11.6.4.2 C~~*C~~H~~NZSIO Cd4*C68H74NzSelo Cd4GeS6 Cd4GeS6 reaction to form CdIz + GeIz: 3.1 1.3.2 Cds*Cz4HsoIOizSiz3+ Cds*C96HsoS Cdio*C3zHsoO16S16~+ Cd lo*C7zHmSI 6 Cd io*C96HsoS16Ted4Cd I o*C96H80Se204Cdio*Ci izHizxN4Sz0 Cdi7*Ci68H140S3~~Cd3z*Czi6Hi8oSso Ce Ce reaction with 0 2 : 3.8.2.1.1 Ce*C14HzoN3014 Ce*C36H6906 Ce*C48H9306 Ce*C48Hi08C13016P4 Ce*Cs4HiosO6 Ce*C7zHmC13016P4 CeC13 CeC13 reaction with n-CllHz3COONa, nClsH31COONaand n-CnH3sCOONa: 3.8.2.10.1 CeC130iz Cr[C10413 reaction with (C~HS)~PO: 3.8.2.6.1 reaction with (n-C4H9)3PO: 3.8.2.6.1 Ce*H 12N301s CeKSe4 K[Ce(Sez)zl formation: 3.8.4 CeO CeO formation: 3.8.2.1.1 CeOi~o-1.70 CeOiso-1.70 formation, structure: 3.10.2.2.2 CeOi.72-2.00 CeOi.7z-z.oo formation, structure: 3.10.2.2.2
398 CeOz CeO2 formation: 3.8.2.1.1 Ce701z Ce7012 formation, structure: 3.10.2.2.2 CeYOl6 Ce9016 formation, structure: 3.10.2.2.2 Ce110zo Cel1020 formation, structure: 3.10.2.2.2 Cet6030 Ce16030 formation, structure: 3.10.2.2.2 Ce190~ Ce19034 formation, structure: 3.10.2.2.2 CezYOsz 0s2Ce29 formation, structure: 3.10.2.2.2 Ce39070 Ce39070 formation, structure: 3.10.2.2.2 Ce4007z Ce40072 formation, structure: 3.10.2.2.2 Ce620112 Ce62OI 12 formation, structure: 3.10.2.2.2 Cl*A104 Cl*AuSe Cl*AuTe2 CI*CF3Se Cl*C2H7HgN204Se CI*C2H7HgN2Se Cl*C2H7Hg04N2Se Cl*C2HsHg2N4Se2 CI*C4HsCuSe2 Cl*CsHsCrN202 C1*Cs MnOs CI*C505Re CI*C~HI~AUP Cl*C7H5Fe02 Cl*CsHsM003 Cl*CsH503W Cl*CsH904Rh2S Cl*CsH 1sCuTe2 CI*C11H22NiPS2 c1*cI lH27Ifi4P3 C1*C12H36AgNsOsP2 Cl*CisHI iN3Pt+ Cl*C15H210& Cl*ClsH35Li206Re c I * c l6H I 4cUOzs4
Compound Index Cl*C17H41IrP3 CI*CISHISAUP CI*CisHIsAuPS CI*CisHlsAuPSe Cl*C19HlgAuN2PSe Cl*C2iH3iM0204 Cl*C22H21Ir03P2 CI*C~SHZIF~II~~P~ Cl*C27H261fl3P2 Cl*C27H54N3NiS6 C1*c3oH26F6~4Pz Cl*C37H3oAs2Ir03 CI*C~~H~OI~N~O~P~ Cl*C37H3oIrOPz CI*C37H3oIr03P2 Cl*C37H30IrP2 Cl*C37H3oIrP20 CI*C3gH3503P2Pt Cl*C40H3oAs2FsIr04 C1*C4oH3oF6Ifl4P2 C~*C~~H~OAU~FIO.S~S~ CI*CS~H~SH~O~P~ Cl*CssH4500sP3 Cl*C96HsoSI 6Zns ClCU CUCl copper-oxygen adducts formation: 3.7.2.1.2 formation of CuOBu-t: 3.7.2.7.1 reaction of 3.7.3.6 CICuSe2 CuClSez synthesis: 3.1.4.2.2 ClCuTe CuClTe synthesis: 3.7.4.2.2 ClCuTe2 CuClTe2 synthesis: 3.7.4.2.2 CIFOzS SOiClF solvent: 3.9.2 solvent in reaction of KrF2 and B(OTeFd3: 3.9.4 Cl*H04 Cl*HioOsRu CI*HI 2CoN5 CI*HI~NSORU Cl*HlsCoNs CIHg04 Hg2[C10412 reaction with (CsH5)3PO: 3.7.2.4.1 CIK KCl F-centers: 3.10.1.1.1
Compound Index ClLi LiCl formation from CuCl and LiOBu-r: 3.1.2.1.1 ClNO NOCl formation from Nz04 and ZnClz: 3.7.2.6.2 ClNa NaCl formation from ZnClz and NaOEt: 3.1.2.1.1 CIV
vc1
reaction with CH30H: 3.8.2.4.1 reaction with CzH50H: 3.8.2.4.1 reaction with X3H7OH: 3.8.2.4.1 reaction with s-CdH90H: 3.8.2.4.1 reaction with C ~ H I I O H3.8.2.4.1 : reaction with n-C3H70H: 3.8.2.4.1 reaction with n-C4H90H: 3.8.2.4.1 Clz*CH4NiO CIz*CS C12*C2HsHgNzSez Clz*C3HaNiO C12*C4HsHgSe Clz*C4H9CdOz Clz*C4HloHgOz C12*C4HloNiO C~Z*C~HIZCOOZ C~Z*C~HIZO~SZW CIz*C404Rhz C~~*C~H~CUNO Clz*CsH5Mo Clz*C5HsW CIZ*C~HIZN~O Clz*C6H7Ti Clz*CsH 12cUo3 C1z*C6Hi4HgO3 C~Z*C~HI CIz*C7HioM00z CIz*C7HloOTi Clz*C7HloOzW C12*CsH1604SzW Ch*CsHisHg04 C~Z*C~HZZ~~V CIZ*C~H~~CUOIZS~ Clz*CloHioM~ C12*CloHloM00 CIz*CloH1oNb CIZ*CIOHIOOW CIz*CloHloTi Clz*CloHIoV CIz*CioHioW Clz*CloHloZr C12*CioH14M004
399
400
Compound Index
Ch*C36H3oP2Se2Hg2 CI~*C~OH~~MON~P~ C12*C48H4&Zn44CI~*C~~H~~AS~COOI~ CI~*C~~H~~AS~F~OI~ CI~*C~~H~~AS~M~OI~ CI~*C~~H~~AS~N~OI~ C~~*C~-WOOI~P~ C12*C52H52FeOI 2P4 C12*C52H52MnOnP4 C12*C52H52Ni012P4 CI~*C~~H&S~COOI~ CI~*C~~H~AS~F~OI~ C12*C72H&s4NiO I 2 C12*C72HmC0012P4 Ch.*C72HmFe012P4 CI~*C~~H~H~OI~P~ C12*C72HmMnO12P4 C12*C72HmNi012P4 Ch*C72HmO1zP4Zn C12*Cd C12*CdOs CIZCO coc12 reaction of 3.8.4 reaction with AgOOCCF3: 3.8.2.10.1 reaction with (CH3)zSO: 3.8.2.6.1 reaction with 18-C-6: 3.8.2.7.1 reaction with CH30Li, C2H50Li and iCsH70Li: 3.8.2.10.1 reaction with sdc-6: 3.8.2.7.1 c12coos CoIC10412 reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CH~)(C~HS)~PO: 3.8.2.6.1 reaction with (CH3)3AsO: 3.8.2.6.1 reaction with (CH3)(CaHs)2AsO: 3.8.2.6.1 reaction with [(CH3)2N]3PO: 3.8.2.6.1 reaction with (CH3)3AsO: 3.8.2.6.1 reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CH3)2SO: 3.8.2.6.1 reaction with (C&)3AsO: 3.8.2.6.1 reaction with (C&,)$O: 3.8.2.6.1 c12cu CUCl2 formation from CuCl and 0 2 : 3.7.2.1.2 reaction of 3.7.3.6 reaction with SbC15 and CH30CH2CH20CH3: 3.7.2.5.1 reaction with C5H5NO: 3.7.2.4.1 reaction with CH3O(CH2CH20)2CH3 in the presence of SbC15: 3.7.2.5.1 reaction with CH30(CH2CH20)3CH3 in the presence of SbC15: 3.7.2.5.1
reaction with CH30(CH2CH20)5CH3 in the presence of SbCIS: 3.7.2.5.1 reaction with CF3COCH2COCH3 and NH40H: 3.7.2.5.1 reaction with 1542-5 and 18-C-6: 3.7.2.5.1 Cl2CuOs CU[C10412 reaction with [(CH3)2N]3PO: 3.7.2.4.1 reaction with (CH3)2SO: 3.7.2.4.1 reaction with (CH3)3PO and (CH3)3AsO: 3.7.2.4.1 reaction with C5H5NO: 3.7.2.4.1 ClzFeOs FeIC10412 reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CH3)(C&)2PO: 3.8.2.6.1 reaction with (CH3)3AsO: 3.8.2.6.1 reaction with (CH~)(C&)~ASO:3.8.2.6.1 reaction with [(CH3)2N]3PO: 3.8.2.6.1 reaction with (C&)3AsO: 3.8.2.6.1 reaction with (CsH5)3PO: 3.8.2.6.1 C12*HlzCoN4 C~~*HI~COO~ C1zHg HgCh reaction with CH3O(CH2CH20)2CH3: 3.7.2.5.1 reaction with CH3O(CH2CH20)3CH3: 3.7.2.5.1 reaction with CH3O(CH2CH20)4CH3: 3.7.2.5.1 reaction with CH3OCH2CH20CH3: 3.7.2.5.1 reaction with dibenzo-18-C-6: 3.7.2.5.1 reaction with H2S: 3.7.3.2 reaction with 18-(2-6: 3.7.2.5.1 ClzHgOs Hg[C10412 reaction with C5H5NO: 3.7.2.4.1 reaction with (CH3)2SO: 3.7.2.4.1 reaction with (CsH&PO: 3.7.2.4.1 C12Mn MnC12 reaction of 3.8.4 reaction with AgOOCCF3: 3.8.2.10.1 ClzMnOs Mn[C1041z reaction with (CH3)zSO: 3.8.2.6.1 reaction with [(CH3)2N]3PO: 3.8.2.6.1 reaction with MePhzPO: 3.8.2.6.1 reaction with Me3AsO: 3.8.2.6.1 reaction with Me3PO: 3.8.2.6.1 reaction with MePhlAsO: 3.8.2.6.1 reaction with Ph3AsO: 3.8.2.6.1 reaction with Ph3PO: 3.8.2.6.1
Compound index CIzNi NiC12 reaction with AgOOCCF3: 3.8.2.10.1 reaction with CH3OLi, CzHsOLi, nC3H70Li, i-QH7OLi and t-C4H90Li: 3.8.2.10.1 reaction with 18-C-6: 3.8.2.7.1 reaction with (CH3)zSO: 3.8.2.6.1 C12Ni08 Ni[C104]2 reaction with (CH3)2SO: 3.8.2.6.1 reaction with [(CH3)2N]3PO: 3.8.2.6.1 reaction with (CH3)3AsO: 3.8.2.6.1 reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CH~)(C~H~)ZPO: 3.8.2.6.1 reaction with (CH3)3AsO: 3.8.2.6.1 reaction with ( C H ~ ) ( C ~ H ~ ) ~ A 3.8.2.6.1 SO: reaction with (C&j)3AsO: 3.8.2.6.1 reaction with (C&)3PO: 3.8.2.6.1 ClzNpO NpOC12 formation by solid state reactions: 3.8.2.8.1 C120Pa PaOC12 formation by solid state reactions: 3.8.2.8.1 C120Th ThOC12 formation by solid-state reactions: 3.8.2.8.1 ClzOTi TiOC12 formation by solid-state reactions: 3.8.2.8.1 ClZOU LJoc12 formation by solid state reactions: 3.8.2.8.1 CI20Zr
zroc12
formation by solid state reactions: 3.8.2.8.1
c12ozu
UOzCl2 formation from uc16: 3.8.2.8.1 ClzOsZn Zn[C10412 reaction with (CH3)zSO: 3.7.2.4.1 reaction with [(CH3)2N]3PO and (C&5)3PO: 3.7.2.4.1 ClzPd PdC12 reaction of 3.8.4
401
402
Compound Index
C~~*C~XH~OL~OZZ C~~*C~~H~OASZN~O~ CI~*C~~H~OMOO$'Z CI~*C~~H~ON~O~PZ CI~*C~~H~~OPZR~ cl3*C36HlosCrN1 x 0 1xP6 C13*C36HlosFeN1 8 01xp6 Cl3*C38H33NPzRe Ch*C48HiosCeO16P4 Cb*C48Hl0&*16P4 C13*C48HlosFeOi6P4 C13*C72H60Ce016P4 cI3*C7zHmC* i6p4 CI3*Ce CI3*Ce012 C13Cr CrcI3 reaction of 3.8.4 reaction with AgOOCCF3: 3.8.2.10.1 reaction with CH30H: 3.8.2.4.1 C13C1-012 Cr[C10413 reaction with (C&)3PO: 3.8.2.6.1 reaction with (n-C4Hg)3PO: 3.8.2.6.1 reaction with OP[N(CH3)2]3: 3.8.2.6.1 CI3Er ErC13 reaction with AlC13 and i-C3H70K: 3.8.2.10.1 C13Er012 Er[C10413 reaction with dibenzo-18-C-6: 3.8.2.7.1 C13Fe FeC13 reaction with AgOOCCF3: 3.8.2.10.1 reaction with CF3COCHzCOCH3 in presence of CH3COONa in H20: 3.8.2.7.1 C13FeOlz Fe[C10413 reaction with (n-C4H9)3PO: 3.8.2.6.1 reaction with OP[N(CH3)2]3: 3.8.2.6.1 reaction with (CH3)zSO: 3.8.2.6.1 Cl3Gd GdCI3 reaction with AlCl3 and i-C3H7OK 3.8.2.10.1 C13*H603Rh CI~HO HoCl3 reaction with AIC13 and i-CsH70K: 3.8.2.10.1 Cl3La Lac13 reaction with n-CllH23COONa, n-
Compound Index C14*CzoH3oRh2 C~~*C~OH~ORUZ c14*c2OH36CO206 C~~*C~OHWN~~O~IP~U C~~*C~~H~OO~PUS~ C14*C36H3003S3U C~*C~OH~ORU~ C14*CmH4203S3Th C14*CmH420&,U C14FezVS43WWFeC121213synthesis of 3.8.3.6.1 C14Fe4S42[Fe4S4C14]2synthesis of: 3.8.3.6.1 C14*HAu C14*HzMoOzCI~*H~~MO~O~P~S~ C14*H 18Mo309S.4 Cl4Hf HfC14 reaction with CF~COCHZCOCF~ in CC4: 3.8.2.7.1 reaction with CH3COCHzCOCH3 in presence of CsHloNH in CzH50H: 3.8.2.7.1 C14KzPt K2PtC14 reaction of 3.8.4 reactivity with polysulfido anions: 3.8.3.6.2 C14Mo MoC14 reaction with CH3COCH2COCH3: 3.8.2.7.1 C14MoO MOC140 hydrolysis to M0042-: 3.8.2.9.1 C14MoSe MoSeC14 formation: 3.8.4 C14M03S7 M03S7C14 precursor to Mo&j clusters: 3.8.3.6.1 CWp NpCh reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CzH5)zSO: 3.8.2.6.1 C140Re ReOC14 reaction with t-CdH9OLi and i-C3H7OLi: 3.8.2.10.1
c4ow
WOc4 formation from wc16 and ,302: 3.8.2.8.1
403
C14016u U[C10414 reaction with OP[N(CH3)2]3: 3.8.2.6.1 C14Pa PaC14 reaction with (CH3hPO: 3.8.2.6.1 C14PU hC14 reaction with (C6Hs)zSO: 3.8.2.6.1 CI4SW
wsc4
reactivity towards thiols: 3.8.3.6.3 C14SeTa TaSeC14 formation: 3.8.4 C14SeW WSeC14 formation: 3.8.4 C14Th ThC14 reaction with CH3COCH2COCH3in presence of CsHloNH in C2H50H: 3.8.2.7.1 reaction with (CH3)zSO: 3.8.2.6.1 reaction with (CzH5)zSO: 3.8.2.6.1 reaction with (a-CloH7)zSO: 3.8.2.6.1 reaction with (CH3)3PO: 3.8.2.6.1 C14Ti Tic14 reaction with CH~COCHZCOCH~: 3.8.2.7.1 reaction with CzH50H: 3.8.2.4.2 reaction with C2H50Na: 3.8.2.10.1
c14u
uc4
reaction with (CH3)3PO: 3.8.2.6.1 reaction with (CH3)zSO: 3.8.2.6.1 reaction with (CzH5)zSO: 3.8.2.6.1 reaction with C6H5)2SO: 3.8.2.6.1 reaction with (a-CloH7)zSO: 3.8.2.6.1 reaction with (CF3)3CONa: 3.8.10.2.1 reaction with sdc-6: 3.8.2.7.1 c14v vc14 reaction to form [V(Hz0)6]3+and vo43-: 3.8.2.9.1 reaction with CH3COCHzCOCH3: 3.8.2.7.1 reaction with CzH50H: 3.8.2.4.2 c14w wc14 reaction with CH3COCHzCOCH3: 3.8.2.7.1 reaction to form WOC14: 3.8.2.8.1
404
Compound Index
CI4Zr zrc4 reaction with CF3COCH2COCF3 in CC4: 3.8.2.7.1 reaction with CH~COCHZCOCH~: 3.8.2.7.1 reaction with CH3COCH2COCH3 in H20: 3.8.2.7.1 reaction with CH3COCH2COCH3 in presence of CsHloNH in C2H50H: 3.8.2.7.1 reaction with i-C3H7ONa: 3.8.2.10.1 Cls*C12HsHgO C15*C13H7HgO C15*H20Ru CIj*Nb ClsMo MoCl5 reaction with (CH3)zSO: 3.8.6.2.3 reaction with C4H80: 3.8.2.6.3 reaction with C4H802: 3.8.2.6.3 reaction with (C~H~)JPO: 3.8.6.2.3 reaction with (C6H5)zSO: 3.8.6.2.3 reaction with Li2S: 3.8.3.6.1 reaction with KzE2: 3.8.4 methanolysis: 3.8.2.4.2 CbNb NbCl5 reaction with K2Te4: 3.8.4 reaction with CH30Li: 3.8.2.10.1 reaction with [(CH~)ZN]~PO: 3.8.2.6.3 reaction with excess (CH3)2SO: 3.8.2.6.3 reaction with excess (CH3)2NCON(CH3)2: 3.8.2.6.3 reaction with excess ( C ~ H ~ ) ~ A S O : 3.8.2.6.3 reaction with excess (C6&,)3PO: 3.8.2.6.3 reactivity towards sulfides: 3.8.3.6.1 reaction to form NbOCI3: 3.8.2.8.1 hydrolysis to [Nb6019]8-: 3.8.2.9.1 ClsPa PaCl5 reaction with CH~COCHZCOCH~: 3.8.2.7.1 C15Re ReCls reaction to form Re02 and ReOd-: 3.8.2.9.1 reaction with Te: 3.8.4 ClsTa TaCls reaction with [(CH3)2N]3PO: 3.8.2.6.3 reaction with Li2S: 3.8.3.6.1 reaction with CH3OLi: 3.8.2.10.1
COmDOUnd Index
405
CO*H303 Co*H12C12N4 CO*Hl2Cl206 Co*H I 2C1Ns CO*HI~N~~+ Co*H1&"0 coo coo formation: 3.8.2.1.1 formation from Co oxidation: 3.8.2.9.2 homogeneity range: 3.10.1.5.1 homogeneity range: 3.10.1.5.2 cool.~t.olz coo1 .oo0-1.012 formation, structure: 3.10.2.2.1 coo2 coo2 formation: 3.8.2.1.1 cos cos formation: 3.8.3.1.1 synthesis of: 3.8.3.6.1 cos2 cosz formation: 3.8.3.1.1 COSe COSe reaction of 3.8.4 C02Ti
OTiCO matrix isolation: 3.8.2.1 1.3 Co2*Ba3Fe24041 cO2*c808 Co2*C1oHlsOlz CO~*CI~HION~O~S~ C02*CnH24Br406 Co2*Ci2Hz4Cb06 CO~*CI~H~OS~~CO~*CI~H~~A~N@&~+ CO2*C12H36Br406S6 COZ*C12H36C1406S6 CO~*C~OH~OS~~ COZ*C~OH~~N~~~S~ CO2*C2oH36C1406 Co2*C36H3&2Co2*H3oN I 0 0 ~ 3 COzN8024 C02(N03)8 formation from CO~(CO)S: 3.8.2.8.3 c0203
cOZ03
formation: 3.8.2.1.1 Co205Sr2 Sr2C0205 structure: 3.10.3.2.1.4
406
Compound Index Cr*C15H2106 Cr*Ci6H3604 Cr*C18H3802 Cr*C 1gH42C1303 Cr*ClsH42N40 Cr*C27&603 Cr*C31H6504 Cr*C36H 108C13N18018P6 Cr*C40Hs&iOs Cr*C48HI osC130I 6p4 Cr*C7zH6oC130i6p4 Cr*CI3 Cr*C13012 Cr*HI 1 0 6 Cr*H1206 CrKSz KCrSz deintercalation: 3.1 1.6 water uptake by oxidative deintercalation: 3.11.6.1.5 CrKSez KCrSez deintercalation: 3.1 1.6 water uptake by oxidative deintercalation: 3.11.6.1 .5 CrLa1.9S3.9 (LaSh.9CrSz synthesis of: 3.1 1.4.2 CrNsOis Cr(N03)6 formation from Cr(C0)6: 3.8.2.8.3 CrNaSz NaCrS2 formation: 3.8.3.1.1 CrNazO4 Na2Cr04 formation from Cr oxidation: 3.8.2.9.2 CrOz
cro2
crystallographic shear in: 3.10.3.1.1 formation: 3.8.2.1.1 metallic conduction: 3.10.1.1.1 reduction of: 3.10.1.5.3 CrO3 0
3
formation: 3.8.2.1.1 Cr04 Cr(02)2 matrix isolation: 3.8.2.1 1.3 CrS CrS formation: 3.8.3.1.1 CrSz CrS2 formation by deintercalation: 3.1 1.6
Compound Index metastable phase: 3.1 1.6 CrSez CrSe:! formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 Crl.ls*Nao.34Sez Cr2*C14H1004Se2 Cr2*Cl6HlOO6 Cr2*C18HzsNzOzSz C~~*CISH~SS~ Cr2*Ca04 CrzKzO7 KzCr207 reaction with NaS2CNR2: 3.8.3.4.2 CrzO3 (3203
formation: 3.8.2.1.1 formation from Cr oxidation: 3.8.2.9.2 reaction with TiO2: 3.10.3.1.1 CrzS3 CrzS3 formation: 3.8.3.2.1 Cr3Se~43[CrdSe4)613formation: 3.8.4 Cr3Te243[Cr3(Te4)6I3formation: 3.8.4 Cr4*C20020Te22CrsNaSes NaCrsSes deintercalation: 3.1 1.6 deintercalation: 3.1 1.6.4.1 CrsSe8 CrsSes formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 CrsSesT1, T1,CrsSeg deintercalation: 3.1 1.6.4.1 Cr6*Ci@ laTee2Crx*CNb2S2 Cr,NbSz CrxNbSz synthesis of 3.11.4.2 CsN03 CsNO3 reaction with XeOF4: 3.9.2 CsNbO7Tiz CsTizNbO7 structurehynthesis: 10.3.2.4.6 C~o.33M003 Cso.33Mo03 structurehynthesis: 3.10.3.2.4.3
407
C~.sMsz Cso.sMS2 synthesis of 3.1 1.7.2 Csz*C%~+xNb6024 CS2*clfjPU cSzMOs016 CS2M05016 structure: 3.10.3.2.1.5 CSZMWOZZ Cs2M07022 structure: 3.10.3.2.1.5 CSZMO~O~~+I CSZMO~O~~+I structure: 3.10.3.2.1.5 CS2046UlS CS2u15046 oxide containing U06 octahedra: 3.10.3.4.3 Cs2Pd3S4 CszPd3S4 ion exchange: 3.1 1.6.2 water uptake by oxidative deintercalation: 3.1 1.6.2 CS2Pt3S4 CS2Pt3S4 ion exchange: 3.1 1.6.2 water uptake by oxidative deintercalation: 3.11.6.2 CS3M04016P3 CS3M04P3016 structure: 3.10.3.3.5.3 cu
cu
active metal powder: 3.7.2.8 reaction with H20 vapor at dull red heat: 3.7.2.2.1 reaction with 0 2 : 3.7.2.1.1 Cu*BzFs Cu*BazOsTI Cu*Ba206T12 C~*Ba,La2-~04 Cu*Bi20&2 Cu*BrSe3 Cu*BrTe Cu*BrTeZ Cu*Br2 Cu*CH3 Cu*CH30 CU*C~HI~H~N~S~~ Cu*C2H140N6Se2 CU*C204 Cu*C4H&1Se2 Cu*C4H90 Cu*C4H9Te Cu*C4H12NTe4
408
Compound Index uptake of polyoxyethylene: 3.1 1.6.2 CuFeLiS2 LiCuFeS2 cumobility: 3.1 1.6.2 lithium deintercalation: 3.11.6.2 CuFeNaS2 NaCuFeSz structure: 3.1 1.6.2 CU*H~MO~NS~ Cu*H4NS4 Cu*HiiOs CU*H 12F606Si CU*H1206 CuISe3 CuISe3 synthesis: 3.7.4.2.2 CuITe2 CuITe:! synthesis: 3.7.4.2.2 CUI2 CUI2 reaction with C5H5NO: 3.7.2.4.1 CuLazOs La2Cu04 structure: 3.10.3.2.1 CuLa2-,04SrX La2-,SrxCuO4 structure: 3.10.3.2.1 CuN206 WN03)z
formation from Cu and N204: 3.7.2.6.1 reaction with C&i$H and amines: 3.7.3.2 CuN309[CW03)31formation by R4NCI and N204: 3.7.2.6.1 CUO CUO formation: 3.7.2.1.1 formation from CuCl and 0 2 : 3.7.2.1.2 formation of Zn and N02: 3.7.2.6.1 formation from Cu and Na2Oz: 3.7.2.7.2 ozone formation: 3.7.2.1.2 CUOO.S0ooo.5016 ~~~0.5ooO.5016
formation, structure: 3.10.2.2.1 cu02 Cu(q 1-02)(matrix-isolated species) formation: 3.7.2.1.1 CuO3Sr2 SrzCuO3 structure: 3.10.3.2.1 CuO3Te CuTeO3 formation: 3.7.4.2.2
Compound Index cuo4 cu-02 matrix isolation: 3.7.2.8 cUo4
CU(O;?)2 matrix isolation: 3.7.2.8 Cu04Se CuSe04 formation: 3.7.4.2.2 cu08Re2 Cu[Re0412 reaction with (C&)3PO and (C&)3AsO: 3.7.2.4.1 cus
cus
formation: 3.7.3.1.1 formation: 3.7.3.6 solubility: 3.7.3.2 cus3
cus3
formation: 3.7.3.2 cus4
cus4
formation: 3.7.3.3 cus4LCuS41formation: 3.7.3.6 CuS4Ti2 CuTi2S4 deintercalation: 3.11.6 CuS4Ti2 Cu[Ti]2S4 deintercalation of copper: 3.1 1.6.4.1 CuS& [Cu(S4)213formation: 3.7.3.6 CuSe CuSe Cu-Se system: 3.7.4.1.1 formation: 3.7.4.3.1 formation: 3.7.4.4.2 CuSe2 CuSe;? Cu-Se system: 3.7.4.1.1 CuTe CuTe Cu-Te system: 3.7.4.1.2 formation: 3.7.4.1.3 formation from polychalcogenide: 3.7.4.6.2.1 CuTe2 CuTe2 formation: 3.7.4.1.2 Cuo.asNbSz Cuo.66NbS2(2H)
409
thermal decomposition: 3.1 1.6.1.2 C~o.dbl+xS~ C~O.~~N~I+XS~(~R) ion ordering: 3.11.6.1.2 Cuo.66SzTa CUo.66TaSd2H) thermal decomposition: 3.11.6.1.2 Cuo.66SzTal+x CUO.~~N~I+XSZ(~R) deintercalation: 3.1 1.6.1.2 CUO.~*CN~~S;? cu1.97s cu1.97s
from sulfidation of Cu with S : 3.1 1.5.2 CU2-,S CU2-xS formation of 3.1 1.4.2 from sulfidation of Cu: 3.1 1.4 Cu;?*Ba;?CaHgO6 Cu;?*Ba;?Ca07TI Cu2*Ba;?CaO8T12 CU~*C~H~S~CUZ*C~H;?~B;?F&"~S~ C~z*CioHzoC140s CU~*CI~H~OB;?F~N~S~ cU;?*ci8H36N I 204S7 Cu2*C32H44Se4W CUz*C4xH7~016SsCu2*CaLaOsSr cu20
cuocu
formation from Cu and H20 at dull red heat: 3.7.2.2.1
cu20
CU20 catalysis of propylene oxidation: 3.7.2.1.3 formation: 3.7.2.1.1 formation from Cu and (NO or SO;?): 3.7.2.6.1 homogeneity range: 3.10.1.5.1 reaction of 3.7.3.6 cu2s
cu2s
exchange reaction: 3.7.4.2.1 formation: 3.7.3.1.1 formation: 3.7.3.6 formation from Cu and SO;?:3.7.2.6.1 solubility: 3.7.3.2 cuzs3 CWS3 formation: 3.7.3.2 cu2ss CUZS5 formation: 3.7.3.2
41 0
Compound Index c~zo*CnH iospi 2s 13 C~29*CiosH252PnSels CU~O*C~OEH~S~PI~S~~~ CU~O*CI~~H~~~PI~S~IX C~o*C132HnoP22 Cux*CNb2S2 CU~MWSLI CUxMO6S8 from reaction of Cu, Mo and S: 3.1 1.7.2 Cu,SzTa CuxTaS2 ion ordering: 3.1 1.6.1.2 Cu,SzTi CuxTiS2 formation by electrochemical intercalation: 3.1 1.6.1.2 CUxS2V
cuxvs2
structure transformation: 3.1 1.6.1.2 Cu,Se2Ti CuxTiSe2 structure transformation: 3.1 1.6.1.2 Cu,SezV CuxVSe2 structure transformation: 3.1 1.6.1.2 Cu,Li,Mo,& LixCUyM06S8 cointercalation of two cations: 3.11.6.4.2 CuyLixMo&e8 LixCUyM06Se8 D D0.36M003 D0.36M003 structure: 3.10.3.2.4.2 Di.asMOO3 D1.68M003 structure: 3.10.3.2.4.2 DY DY reaction with 0 2 : 3.8.2. 1 DYO DYO formation: 3.8.2.1.1 DYz03 DY203 formation: 3.8.2.1.1
E Er Er reaction with 0 2 : 3.8.2.1.1 Er*C2oH26C13019 Er*C36Hx4A13012 Er*C13
COmDOUnd
Er*C13012 ErO El0 formation: 3.8.2.1.1 ErzO3 Er203 formation: 3.8.2.1.1 Eu ELI reaction with 0 2 : 3.8.2.1.1 EuO EuO formation: 3.8.2.1.1 EuS EuS formation: 3.8.3.2.1 EW03 EWO3 formation: 3.8.2.1.1 Eu204 Sr SrEu204 structure: 3.10.3.3.3 F F*CC13 F*CH30Xe F*C36H44N4Ti F*C102S F*H F*HO3S F*HS3 FHg Hg2Fz reaction with H20: 3.7.2.2.2 FN02 FN02 removal: 3.9.2 FNa NaF purification of XeOF4: 3.9.2 FNb31077 Nb31077F crystallographic shear in: 3.10.3.1.3 F*TH F~*C~H~~PRUS Fz*C36H44N4Ti F2*H02P Fzfi fiFz reaction with B(OTeF5)3: 3.9.4 F2MoSe MoSeFz formation: 3.8.4 FZNbSe NbSeFz formation: 3.8.4
Index
F20Se OSeF2 reaction with XeF2: 3.9.3 F20Xe OXeF2 formation: 3.9.2 F20zXe 02XeF2 decomposition: 3.9.2 formation: 3.9.2 hydrolysis: 3.9.2 F203SXe FXeS02F preparation: 3.9.3 reaction with AsF5: 3.9.3 F~03Xe 03XeF2 formation: 3.9.2 F206Sz (FS03)00(S02F) product in reaction of F5XeOS02F and excess HOSOzF: 3.9.3 Fz06SzXe Xe(OS02F)2 preparation: 3.9.3 FzRn RnF2 possible identification: 9.3.4 FzSeTa TaSeFz formation: 3.8.4 FzSeW WSeF2 formation: 3.8.4 F2Xe XeF2 reaction with CH3C(OH)NH2+,AsFes-: 3.9.3 reaction with CH30H: 3.9.2 reaction with cis-(HO)~TeF4:3.9.3 reaction with fluorinated sulfonates and carboxylates: 3.9.2 reaction with general oxyacids: 3.9.3 reaction with HOS(F)02: 3.9.3 reaction with HOSeF5 and HOTeF5: 3.9.3 reaction with (Io2F4)2: 3.9.2 reaction with SeOF2: 3.9.3 removal: 3.9.2 F3*B F3*CAg03S F3*CCISe F3*CH03S F3*C2H02 F3*C7Mn07 F3*C707Re
41 1
41 2
Compound Index
F~*C~H~BOSSW F3 *C12H 1sOZn F~*CI~H~~BO~SW F3 * c i xH36AgN209S F3*C37H3i PzPt F3*C54H46hPt F3MoSe MoSeF3 formation: 3.8.4 F3NbSe NbFeF3 formation: 3.8.4 F3SeTa TaSeFs formation: 3.8.4 F3SeW WSeF3 formation: 3.8.4 F4*AgB F4*CO3SXe F4*CloH14BMn02S F4*C 1xHzoAgB02 F4*H202Te4 F4K2Ni KzNiF4 intergrowth to form homologous series: 3.10.1 S.4 structure: 3.10.3.2.1.1 F4MoSe MoSeF4 formation: 3.8.4 F4NbSe NbFeF4 formation: 3.8.4 F40W woF4 reaction with XeF2: 3.9.2 F40Xe OXeF4 formation: 3.9.2 hydrolysis: 3.9.2 reaction with B(OTeF5)3: 3.9.3 reaction with N2O5: 3.9.2 reaction with nitrates: 3.9.2 reaction with SiO2: 3.9.2 reaction with XeO3: 3.9.2 F4Rn RnF4 possible existence and hyrolysis: 9.3.4 F4SeTa TaSeF4 formation: 3.8.4 F4SeW WSeF4 formation: 3.8.4
Compound Index F6*C39H3003P2Pt F6*c&3oAS2clrfl4 F6*C@H3@rIr04P F~*C~OH~OC~I~~.IP~ F~*C~OH~OII~~~P~ F~*HIzCUO~S~ F6OSeXe FXeOSeFs formation: 3.9.3 FsOTeXe FXeOTeFs reaction with AsF5: 3.9.3 F606SXe FsXe(OS03F) preparation and decomposition: 3.9.3 F606SzXe F4Xe(OS02F)2 withdrawn claim: 3.9.3 F6Rn RnF6 possible existence and hyrolysis: 9.3.4 Fdie XeF6 hydrolysis: 3.9.2 reaction with aqueous base: 3.9.2 reaction with B(OTeFs)3: 3.9.3 reaction with HS03F: 3.9.3 reaction with nitrates: 3.9.2 reaction with P(O)F3: 3.9.2 reaction with Si02: 3.9.2 Fs*B2Cu F E * C ~ H ~ ~ B ~12% CU~N F~*CI~H~@~CU~N& FeIzO4Xe Xe(OIOF4)z formation: 3.9.2 Fs03TezXe OXeF3(OTeFs) identification in mixtures: 3.9.3 FsOsYa Y60sF8 proposed structure: 3.10.3.4.1 Fg*As03SXe2 Fg*C3B06 Fg*C3BOgS3 Fg*C6CIf& Fg*C6FeO6 Fg*C1sH12Fe06 FlO*C403 Fio*ClgHsNi Fio*CzoHI 6Ni Flo*CzoH2oAgNS2 Fio*CzoHzoAuNSz FIO*C~OHZOCUNSZ Flo*C42H3oAu2CISbSe
41 3
FloOzSez FsSeOOSeFs product of decomposition of Xe(OSeF5)z: 3.9.3 FloOzSeTeXe Xe(OTeFs)(OSeFs) formation in solution: 3.9.3 FloOzSezXe Xe(OSeF5)2 formation: 3.9.3 FioOzTez FsTeOOTeFs decomposition product of Kr(0TeFs)z: 3.9.4 product of decomposition of Xe(0TeFs)z: 3.9.3 Flo02TeZXe Xe(OTeFs):! formation: 3.9.3 FroOzWzXe FeOWFs WOF4 formation: 3.9.2 FloOzWzXe XeF2 2WoF4 formation: 3.9.2 FI I*AsOTeXe FllFeOs [Fe( H20)5OH]2+ formation from [Fe(H20)6]3+:3.8.2.2.2 F12*C408Xe Fi2*Cs Fi2*CioHsCOO6 FI2*C i2H I sOsP2Pd FI~*C~ZH~OO~PZP~ FI~*C~EH~OA~~AS~S~X F1203TezXe OXeF2(0TeFs)2 identification in mixtures: 3.9.3 F13*C20SXez F14*C6 FM*CISHIOO~Z~ F1403W3Xe FXeOWFs. 2WOF4 formation: 3.9.2 F15*BO3Te3 FlsKrO3Te3 Kr(OTeFs13 decomposition: 3.9.4 formation: 3.9.4 F1604Te3Xe OXeF(OTeFsh identification in mixtures: 3.9.3 Fi s*C 15H3Cr06 Fis*Ci5H3Mo06 F I 8*ci6H I 6 0 6 u
414 Fl803Te3Xe F3Xe(OTeF5)3 identification in mixtures: 3.9.3 F~o*C~OH~OC~N~S~ F~o*C~OH~OH~N~S~ F~o*C~OH~ON~S~Z~ FzoO~Te4Xe OXe(0TeFsh formation: 3.9.3 F~20dTe4Xe FzXe(OTeF5)4 identification in mixtures: 3.9.3 F23014Yl7 Y17014F23 intermediate phase of 3.10.1.5.5 Fz4*CzoH4HfOs Fz~*C~OH~OXZ~ Fz&TesXe FXe(OTeF5)s identification in mixtures: 3.9.3 F~oOsTesXe Xe(OTeF& formation: 3.9.3 F36*C24H 1 6 0 6 u FxM003-x MoO3-,FX metallic conductors: 3.10.3.4.3 Fx03-xW WO3-xFx metallic conductors: 3.10.3.4.3 Fe Fe reaction with 0 2 : 3.8.2.1.1 Fe*AlCa205 Fe*BaosSz Fe*Br3 Fe*CO3 Fe"CzH40 Fe*C4042Fe*C505 Fe*C6Fy06 Fe*C6H5IO Fe*C7HsC102 Fe*CsHzoS42Fe*CsOsSezWZ+ Fe*CloH606 Fe*CioHi 1N02S2 Fe*ClIHlI Fe*C I 2H36As4ChOI z Fe*C I 2H36C120I 2p4 Fe*CnH36ChO1&6 Fe*C12H36NzSi4 Fe*C 15HI zF906 Fe*C15H2106 F~*CI~H~IS~
Compound Index
-
F~*CZIH~IS~ Fe*C24H2&2Fe*C24H36N I 2% Fe*Cz4HnC12N I 2 0 I 2P4 Fe*C3oH3oN6 Fe*C36H24Ns Fe*C36HiosC13N I 8 0 I 8p6 Fe*C3yH53NdSSi Fe*CaH49P3 Fe*C48H37N40 Fe*C48H10&13016P4 Fe*C5oH41N4 Fe*C5oH41N40z F~*C~~H~ZAS~C~~OIZ F~*C~ZH~~C~~OIZP~ F ~ * C ~ ~ H ~ OI zA S ~ C ~ ~ O Fe*CnH60C1201zP4 Fe*Ca03-, Fe*Cao.sH2,OYSz Fe*Ca2CoO5 Fe*C1208 Fe*CI3 Fe*C13012 Fe*CuKSZ Fe * CuLiS2 Fe*CuNaS2 Fe*F1106 FeH303 Fe(W3 treatment with HzS: 3.1 1.5.1 FeHaa02Sz NaFeSz 2H20 by precipitation from colloidal solution: 3.11.6.3 formation by ion exchange: 3.1 1.6.3 Fe*H 1 2 0 6 FeKSz KFeSz additional Li uptake: 3.1 1.6.3 Cu exchange, structure transition: 3.1 1.6.3 formation: 3.8.3.1.1 formation: 3.8.4 Li exchange, colloid formation: 3.1 1.6.3 synthesis of 3.8.3.6.1 FeK204 K2Fe04 formation from Fe oxidation: 3.8.2.9.2 Fe*LiSn04 FeLizS2 LizFeSz deintercalation: 3.1 1.6 deintercalation: 3.1 1.6.2 FeLi308Sbt Li3FeSb208 structure: 3.10.3.3.3
Compound Index FeMozS3[Fe(MoS4)z13synthesis of: 3.8.3.6.1 FeNaO7Pz NaFePzO7 structure: 3.10.3.3.5.3 FeO FeO formation: 3.8.2.1.1 homogeneity range: 3.10.1.5.2 Fe01.~5-1.zw Fe0i.04-1.zoo formation, structure: 3.10.2.2.1 FeOz FeOz Fe(O2) (matrix-isolated species formation: 3.8.2.1.1 FeOO (matrix-isolated species) formation: 3.8.2.1.1 OFeO (matrix-isolated species) formation: 3.8.2.1.1 FePS3 FePS3 redox intercalation: 3.1 1.6.2 FePSe3 FePSe3 redox intercalation: 3.1 1.6.2 FeS FeS formation: 3.8.3.1.1 synthesis from Fe(OH)3 gels: 3.1 1.5.1 FeSz FeSz formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 metastable product of deintercalation: 3.1 1.6.2 FeTe FeTe formation: 3.8.4 Feo.zsNa0.5604Ti1.7~ Nao.s6Feo.z8Ti1.7204 structure: 3.10.3.3.3 Feo.9~0 Feo.9~0 preparation from Fez03 and Fe: 3.10.1.5.2 Fez*C4HloN404Sz Fez*C606Sz2Fe~*C606Te~ Fez*C606Te32Fez*C606Te& Fez*CsH606Sz Fez*CgH16SszFe2*C1zHloNs04Sz Fez*ClzH30%2-
415
Fez*C 14H1004 Fez*C 14H1602s~ Fe2*C14HzoOzSz Fez*C14H2oS4 Fez*CI 6Hz6Nz04S6 F~~*C~~HZ~NZSZ~+ Fez*C24H36N I zNiS1z Fe2*CxH4002PzTe2 F~z*CZ~H~~NIZ~ZS~~ F~~*C~F~H~OS~ZFe2*C72HssNsO Fe2*C7zH116s4 Fez*C96H7zNsO Fez*Ca04 Fez*Ca205 Fez*C14VS43FezIzN404 Fe2120")4 reaction with S2-: 3.8.3.6.1 FezKzNb4013 KzFezNb4013 structure: 3.10.3.3.2 FezM04 MFe204 structure: 3.10.3.2.2.1 FezN404S~Z[Fe2Sz(N0)412synthesis of: 3.8.3.6.1 FezNajS4 Na3FezS4 mixed valent compound: 3.1 1.6.3 FezNi04 NiFezO4 host spinel: 3.10.2.3.5
magnetic oxides: 3.10.2.3.2 Fez03 Fez03 equilibration to form Feo.920: 3.10.1.5.2 formation: 3.8.2.1.1 Fez03 y-Fe203 defect spinel: 3.10.2.3.2 FezOdSr SrFezO4 structure: 3.10.3.3.3 Fe2S1~2[Fez(S)z(S5)~12synthesis o f 3.8.3.6.2 FezSelz [(Ses)Fe(Sez)Fe(Se)slzformation: 3.8.4 Fe3*C6H1&3Fe3*C9HS09 Fe3*C909Te2 Fe3*C12012TeZ-
41 6
Compound Index Ga048Tiz1 Ga4Ti21048 structure: 3.10.2.2.5.5 Gd Gd reaction with 0 2 : 3.8.2.1.1 Gd*C36Hs&012 Gd*Cl3 GdO GdO formation: 3.8.2.1.1 Gd203 GC.203 formation: 3.8.2.1.1 Ge*AINa04 Ge*Cd& GeIz GeIz formation from chemical mass transport: 3.11.3.2 GeNbllOz9 GeNb 1 1 0 2 9 crystallographic shear in: 3.10.3.1.3 GeOz Ge02 phase formation: 3.10.3.4.2 GeSe,Tel-, GeSexTe from mixtures of the elements: 3.11.7.1 Ge2*C18H&dSe2Si2 Ge2*C18H54CdSi2Te2 Ge2*ClsH54HgSezSiz Gez*C 18H54HgSi2Tez Gez*ClsH54Se2Si2Zn Gez*C18H5&Te2Zn Ge4MnSlG[MnGe4Slopsynthesis of 3.8.3.6.1 Ge4Slo4[Ge&ol4use as ligand: 3.8.3.6.1
G GazO3 Ga203 reaction with TiO2: 3.10.3.1.1 Gaz03 B-GazO3 reaction with TiO2: 3.10.1.3.3 Ga08Ti GaTiO8 structure: 3.10.2.2.5.5
H HAuC14 H[ AuC141 reduction with s2032-: 3.7.3.2. H*CF303S H*C2F302 H*C5Mn05S H*C505SWH*C9Fe3S09 H*C72P4Pt HCI04 ~ 0 ~ 1 0 ~ reaction with XeF2: 3.9.3
Compound Index HF HF removal: 3.9.2 removal: 3.9.3 HFO3S HOS(F)02 reaction with XeF2: 3.9.3 HFSj HFS3 formation: 3.8.3.1.1 HFzOzP HOP(O)F2 reaction with XeF2: 3.9.3 HFsOSe HOSeF5 reaction with XeF2: 3.9.3 HFsOTe HOTeFs reaction with XeF2: 3.9.3 H*KO HKMos016 m 0 5 015OH structure: 3.10.3.3.1 HNaS NaSH equilibrium in water with Na2S: 3.8.3.6.1 HNbOsTi HTiNbOs structurelsynthesis: 10.3.2.4.6 HNbOaTi HTiNbO6 structure: 3.10.3.3.2 HReO4 HRe04 formation from Re and H202: 3.8.2.3.1 H*TF H2*Au02 H2*CsOsSW H~*C~MOZO~S~H2C14M002[MoOC14(0H2)]reactivity toward thiolates: 3.8.3.6.3 HzCIsORu [RuCls(HzO)]z+ formation from [RuCl6]3-: 3.8.2.2.1 HzF40zTe.1 cis-(OH)zTeF4 reaction with XeF2: 3.9.3 HzHgOz Hg(OW2 formation from Hg and NaOH: 3.7.2.7.2 H20 Hz0 reaction with xenon fluorides and oxyfluorides: 3.9.2
HzOz
417
H202 destructive oxidation of metalphthalocyanines of V3+, Cr3+, M+, Co2+, Ni2+, Rh3+,Ru3+, Pd2+, Os4+, Ir3+: 3.8.2.3.1 oxidation of phthalocyanines of Cu, Ag, Zn and Hg: 3.7.2.3.2 reaction with Cu, Ag, Au, Hg, Zn, Cd, Cu(bipy)Z: 3.7.2.3.1 reaction with lanthanide metals: 3.8.2.3.1 reaction with Y, Ti, Zr, Hf, Nb, Ta: 3.8.2.3.1 H~04Se H2Se04 starting material for CuSe04, AgzSeO4, Aua(SeO4)3: 3.7.4.4.2 H~04Te H2Te04 starting material for Ag2Te04: 3.7.4.4.2 ~ ~ 0 ~ 0 9 [Os04(OH)z12formation from 0s: 3.8.2.9.2 HzS H2S reaction of 3.7.3.6 reactions of: 3.1 1.4 reactions of 3.1 1.7.2 reactions with metals: 3.1 1.4 reducing agent, intercalation: 3.1 1.6.1.1 H2S04 acidifying Cu, Ag reactions: 3.7.2.3.1 reagent in phthalocyanines oxidation: 3.7.2.3.2 HZSe H2Se reactions with metals: 3.1 1.4.2 HZTe H2Te reactions with metals: 3.1 1.4.2 H~S+~*C~.~NO.~S~T~ H2y*Cao.sFeOySz H~yKxOyPt4S6 Kx(H20)y[PbS6lxproduct of oxidative deintercalation: 3.11.6.2 ion exchange: 3.1 1.6.2 HzyNao.330ySzTa Nao,33(H20),TaSz exfoliation: 3.1 1.6.1.7 intercalation compounds by flocculation: 3.11.6.1.7 preparation of new: 3.11.6.1.7 starting material for: 3.11.6.1.7 H3*CCu
418
Compound Index
H3*CCuO H3*CFOXe H3*CHgNO3 H3*CLiO H3*CN02 H3*CNaS H~*CCU H3*CCuO H3*CFOXe H3*CHgN03 H3*CLiO H3*CN02 H3*CNaS H3*Ci5CrF1806 H3*Ci5Fi8Mo06 H3*C18LaN206 &COO3 Co(OH)3 formation from Co and H202: 3.8.2.3.1 H~CUMO~NS~ Cu(NH3)Mo& formation: 3.7.3.6 H3*Fe03 HsxNS2Ta (NH~+),(NH~)I-,[T~S~I~ proposed composition of the ammonia intercalation compound: 3.1 1.6.1.6 H4Ag04[Ag(OH)41formation from Ag and NaOH: 3.7.2.7.2 H4AuNS3 NH4AuS3 formation: 3.7.3.2 H4Au04 [Au(OH)41formation from Au and NaOH: 3.7.2.7.2 H4Au04[Au(OH)41formation from [AuCl4]-: 3.7.2.7.1 H4BK DH4 reactions with metal sulfides: 3.1 1.5.2 H4BLi LiBH4 reactions with metal sulfides: 3.1 1.5.2 reaction with WS2: 3.11.7.2 H4BNa NaBH4 reactions with metal sulfides: 3.1 1.5.2 H~*CAUN~S+ H4*CC12NiO H~*CCU~N~S+ H4*CHgO H4*CN2S H4*CO
Compound Index
41 9
420
Compound Index
Compound Index
42 1
Hiz*C6NbS6HI~*C~N~~S~ZHl2*C,&Ti2H12*C702Zn HI2*CsBr4N4U H 12*CsMo208 Hiz*CsN4S6Zn H12*CloBrFsPdS2 H12*CloMoS HIz*C ioMozS4 Hi z*C loSTi Hi2*CioSW H12*CloS2Ti Hi2*C1oZr HI2*c 1 1 F6NiO Hlz*C1lOzZn Hl~*Ci2Cr Hiz*CizNz H12*C13N2NiO3 Hn*C1sFgFe06 H1zCeNs01s Ce[N03]3 6H2O reaction with benzo-15-C-5: 3.8.2.7.1 HlzClCoNs [Co(NH3)5CI]2+ aquation: 3.8.2.2.1 HizCIN50Ru truns-[Ru(NH3)4(NO)C1]2+ precipitation to form [Ru(NH3)4NOOH]2+: 3.8.2.9.1 H~~CI~CON~ [WNH3)4Chl+ aquation: 3.8.2.2.1
H12CI2C006
CoC12 6H20 reaction with C2H50H: 3.8.2.4.1 HizCr06 [Cr(H20)613+ hydrolysis: 3.8.2.2.2 H&uFaO&i [Cu(HzO)6lSiF6 reaction with thiourea: 3.7.3.3 HizCUO6 [C~(H20)612+ hydrolysis: 3.7.2.2.2 HlzFeOs [Fe(Hz0)613+ hydrolysis: 3.8.2.2.2 H1zLaN3015 La[NO& 6H2O reaction with benzo-15-C-5: 3.8.2.7.1 reaction with sdc-6: 3.8.2.7.1 HlzLnN3015 Ln[N03]3* 6h20 (Ln=La-Nd) reaction with dibenzo-18-C-6: 3.8.2.7.1 9
422
Compound Index
Compound tndex
423
424
Compound Index
Compound Index
425
Compound Index
Compound Index
427
Compound Index
Compound Index
429
430
Compound Index Hf02 HfO2 formation: 3.8.2.1.1 reaction with H2S in presence of C: 3.8.3.2.1 HfSz HfS2 formation: 3.8.3.1.1 metallocene intercalation: 3.1 1.6.1.7 synthesis of 3.8.3.6.1 HfS3 HfS3 lithium intercalation: 3.1 1.6.3 HBe2 HfSe2 metallocene intercalation: 3.1 1.6.1.7 HfSe3 HfS3 lithium intercalation: 3.1 1.6.3 HfTe2, HfTeZ-, lithium intercalation of 3.1 1.6.1.1 Hf2S Hf2S formation: 3.8.3.1.2 Hf3K4Te17 hHf3Tel-r formation: 3.8.4
Hg
Hg reaction with 0 2 : 3.7.2.1.1 Hg*Ba2CaCu206 Hg*Ba2Ca2Cu3Os Hg*Ba2Ca3Cu4010 Hg*Br2 Hg*CH3N03 Hg*CH40 Hg*CzF&e Hg*C2F&e2 Hg*CzH4C14N2Sez Hg*C2H6Br212Te Hg*C2H6Se2 Hg*CzH7BrNzSe Hg*C2H7CIN204Se Hg*CzH7CIN2Se Hg*C2H7Cl04NzSe Hg*CzH7N303Se Hg*C~H703N3Se Hg*CzHsBr2N2Sez Hg*C2HsCIzN2Se2 Hg*C2H14CuN6Se2 Hg*C3H602Se Hg*C3HgS+ Hg*CdCoN&e4 Hg*C&Sz
Compound Index
431
Hg*C104 Hg*CIz Hg*C1208 Hg*F Hg*HzOz Hg*HsNloSez HgIz Hgh reaction with 18-C-6: 3.7.2.5.1 HgW4 &Hg% formation: 3.7.3.2 HgNO3 HgN03 formation from Hg and (N204 or NOz): 3.7.2.6.1 HgNzOs HgW" reaction of 3.7.3.6 HgO HgO formation: 3.7.2.1.1 formation from HgzFz and H2O: 3.7.2.2.2 reaction with NaSC6Hs: 3.7.3.6 reduction: 3.7.4.2.1 HgS HgS formation: 3.7.3.1.1 formation: 3.7.3.6 reaction with KzS: 3.7.3.2 solubility: 3.7.3.2 HgSizZ[Hg(S6)zI2formation: 3.7.3.6 HgSe HgSe formation: 3.7.4.1.1 formation: 3.7.4.3.1 formation: 3.7.4.4.1 HgTe HgTe formation: 3.7.4.1.2 formation: 3.7.4.2.1 formation: 3.7.4.3.1 Hg1.19SzTa Hgl.19TaSz intercalate ion ordering: 3.1 1.6.1.2 Hgi.24SzTi Hg I .z4TiSz from reaction of TiS2 and Hg: 3.1 1.7.1 intercalate ion ordering: 3.1 1.6.1.2 synthesis: 3.1 1.7.2 Hgz*CzH60 Hgz*C2HsBrN4Sez
432
Compound Index
Hgz*CzH8CIN4Sez Hg2*C2H&14Sez H~~*C~~H~OC~ZPZS~Z Hgz*C36HiosSii6Te4 HgxS2Ta HgxTaSz intercalate ion ordering: 3.1 1.6.1.2 Ho Ho reaction with 0 2 : 3.8.2.1.1 Ho*C36H84AbOiz Ho*Cl3 HoO HoO formation: 3.8.2.1.1 HoZO3 H0203 formation: 3.8.2.1.1
I,Li,Mo&es-, LixMO6Se8-yIy formation by: 3.1 1.6.4.2 InS2Ta InTaSz intercalate ion ordering: 3.11.6.1.2 In-3.5MoisSi9 In-3sMoisS19 deintercalation: 3.1 1.6.4.2 ion exchange in alkali halide melts: 3.1 1.6.4.2 In-3MotsSi9 In-3MoisSis deintercalation: 3.1 1.6 In-3MolsSe~~ In-3MoisSe19 deintercalation: 3.1 1.6 deintercalation: 3.1 1.6.4.2 Inz-&ixMo&e6 Inz-xLix[Mo6Se61 Li deintercalation: 3.1 1.6.3 InzMo&es h[Mo6Se6l ion exchange in alkali halide melts: 3.11.6.3 InzMo6Teg In2[Mo6Te6] ion exchange in alkali halide melts: 3.1 1.6.3 In2MoisSen InzMo&eig deintercalation: 3.1 1.6 deintercalation: 3.1 1.6.4.2 Ir Ir reaction with 0 2 : 3.8.2.1.1 Ir*Ci iHz7C104P3 Ir*C12H32P4Ses+ Ir*C 13H24C12P Ir*C 13H24PS4 Ir*C 13H24PS5 h*Cl 3H24PS6 Ir*Ci7H4iCIP3 Ir*C2zH21C103P2 Ir*CzsHziCIF604Pz I~*CZ~H~~CIO~PZ I~*C~OHZ~C~F~~~PZ Ir*C37H30AszC103 Ir*C37H30BrO3Pz I~*C~~H~OC~N~O~PZ Ir*C37H3oCIOPz Ir*C37H3oC103Pz Ir*C37H3oCIP2 Ir*C37H30103Pz
Compound Index
K K*CzAuNzSz K*CsH5S K*CeSe4 K*CI K*CrS2 K*CrSe2 K*CuFeS2 K*Cu& K*FeSz K*HMo5016 K*H4B KMoSz KMoSz deintercalation: 3.1 1.6 KNb3015P3 KNb3P3015 structurelsynthesis: 3.10.3.3.5.2
433
KOH KOH reduction of (Ag(OH)4)- to “Ago”: 3.7.2.7.2 Ko.i8*NW4 K0.33M003 K0.33M003 structurelsynthesis: 3.10.3.2.4.3 K0.3Md3 K0.3MoO3 structure: 3.10.3.2.4.3 Ko.3S4Ti3 K0.3Ti3S.i deintercalation: 3.1 1.6 reaction of TiS2 and K in molten KC1: 3.11.7.2 Ko.4M03S4 %.4M03S4 synthesis o f 3.1 1.7.2 &.d+3~Tis h.52Ti6Se8 deintercalation: 3.1 1.6 Ko.7SsVa G.7V6s8 deintercalation: 3.11.6 KO.9M06017 b9M06017 structurelsynthesis: 3.10.3.2.4.3 Kz*C14Pt Kz*C16Ru Kz*Crz07 &*CWSIO Kz*F4Ni Kz*Fe04 Kz*FezNb4013 KzMgzNb4013 KzMgzNb4013 structure: 3.10.3.3.2 &MOO4 KZM004 synthesis: 3.10.3.2.4.3 KzMo3Se13 Kz[MO3(Se)(Sez)61 formation: 3.8.4 KzMo3Se1s K2[Mo3Se(Se2)3(Se3)(Se4)21 formation: 3.8.4 KzNi3S4 K2Ni3S4 water uptake by oxidative deintercalation: 3.1 1.6.2 KZOlOW3 K2W3OlO structure: 3.10.3.3.1 Kz017Tis K2TisOi7
434
Compound Index
K2017Tis (Continued) structure: 3.10.3.3.2 KzPdSelo KdPdSelol formation: 3.8.4 K2PW4 K2Pd3S4 ion exchange: 3.1 1.6.2 water uptake by oxidative deintercalation: 3.11.6.2 K2Pt4S6 K2hS6 water uptake by oxidative deintercalation: 3.11.6.2 ion exchange: 3.11.6.2 K2S4 K2S4 as source of polysulfido anions: 3.8.3.6.2 reactivity toward transition metal carbonyls: 3.8.3.6.2 K2Se K2Se reaction of 3.8.4 K2Se2 K2Se2 reaction of: 3.8.4 K2Se3 K2Se3 formation: 3.8.4 K2Se4 K2Se4 reaction with V 3.8.4 KzSes K2Se5 formation: 3.8.4 K2Tez K2Tez formation: 3.8.4 K i h K2Te4 formation: 3.8.4 K3*C16MO K3017Tis K3TisOI 7 structurehynthesis: 10.3.2.4.6 %*Hf3Tei7 K4*MxTe3 K402SesV2 K4[V202Se2(Se2)(Se4)21 formation: 3.8.4 K402SeloVz K4[V202Se2(Se4)21 formation: 3.8.4 K4PbSezr
K4hSe22 formation: 3.8.4 K4s11Ta2 K4Ta2S I I synthesis o f 3.8.3.6.2 K4S14Ti3 K4Ti3S14 synthesis of 3.8.3.6.2 K4SesU &[U(Se2)41 formation: 3.8.4 K4Te17Zr3 K4Te3Te17 formation: 3.8.4 &*HgS4 K6MogSe27 K6[Mo6(Se)3(Sez)id formation: 3.8.4 Wb4Se22 KdNb4Se4(Se2)91 formation: 3.8.4 K603oTalo.w K6Talo.80030 structure: 3.10.3.3.1 K6.i *
[email protected] K7Nb14+xOd%-x K7Nb14+xP9-x0~ structurehynthesis: 3.10.3.3.5.2 KsMwSe40 Ks[ModSe)4(Sez)isl formation: 3.8.4 KlzM01zSe56
KI~[MOI~S~S(S~~)IS(S~~)~~
formation: 3.8.4 Kn-~o~n+lTinZ[Kn-1Tin03n+il" structure: 3.10.3.2.1 Kn-103n+lVn2[Kn-1 Vn03"+1I" structure: 3.10.3.2.1 Kx*H2yOyPt4S6 KxMoS2 KXMoS2 deintercalation of potassium: 3.11.6.1.1 KxS2Ta KxTaS2 reaction of TaS2 and K in liquid NH3: 3.1 1.5.2 KxS8V6 KxV6S8 deintercalation: 3.11.6.4.1 Kr*F2 Kr*F1503Te3 Kr*o3
Compound Index L La La reaction with 0 2 : 3.8.2.1.1 La*C6HloCON605 La*C~HzoN3014 La*C18H3Nz06 LaCisHdz06 La(K222)2+ electrointercalation: 3.1 1.6.1.7 La*CzoH36N30is La*C36H6906 La*C48H9306 La*Cs4H10506 La*CaCuzO&r La*Cl3 La*HnN3015 LaMn03+x LaMn03+, nonstoichiometric oxide: 3.10.2.3.3 LaN309 La"0313 reaction with cryptand-222: 3.8.2.7.1 Lal.s*CrS3.9 La2-,*BaxCu04 La2-,*CaxCu04 La2-,*Cu04Srx Laz*Cz7H54N90z7 Laz*Cu04 La203 La203 formation: 3.8.2.1.1 La207Zr2 Zr2LazO7 pyrochlore structure: 3.10.2.3.4 LaX*Bal-,03Ti Li*BH4 Li*CH30 Li*C4Hg Li*C4HloO Li*CsH 16B Li*C6H 1sNbO6 Li *C6H1806Ta Li*C40H&rOs Li*CI Li*CuFeSz LiFeSn04 LiFeSn04 structure: 3.10.3.3.3 Li*H4B LiMnOz LiMnOz structure: 3.10.3.2.4.4 LiM11204-~ LiMn204-,
435
charge compensation: 3.10.2.3.2 Li*O4Tiz LiSzV LiVS2 deintercalation: 3.11.6 LiSzZr LiZrSz structural transformation of: 3.1 1.6.1.1 Li0.33Md3 Lio.33Mo03 structure/synthesis: 3.10.3.2.4.3 LiosMSz LiosMSz layers solids from alkali halide melts: 3.11.7.2 Lio.asPbxSz+xV Lio.65(PbS)x(VSZ) intercalation in: 3. I 1.6.1.4 Li0.9M06017 Lio.gM06017 structure/synthesis: 3.10.3.2.4.3 Lil-xNb03-zx Li 1-xNb03-zx Li1+~0sV3 Li~+~Vsos structure: 3.10.3.2.4.1 Li2*CzHdSz Li2*ClsH35CiO.&e LiZ*CU6S17 LiZ*FeS2 LizMo&es LiZ[M06Se6] Li deintercalation colloid formation in nonaqueous solvents: 3.1 1.6.3 Liz0 Liz0 phase formation: 3.10.3.4.2 solid solution: 3.10.3.4.2 Li~07Tij LizTi30.l structure: 3.10.3.3.3 LiZS Li2S reaction of 3.7.3.6 reactivity with metal halides: 3.8.3.6.1 Liz& LizSiz reaction with metal halides: 3.8.3.6.1 Li2Se2 LizSez formation: 3.8.4 LizSes LizSes formation: 3.8.4
436
ComDound Index
LizSea LizSe6 formation: 3.8.4 Li3*FeOsSbz Li4*Cu12Ss Li4013V6 Li4V60 13 structure: 3.10.3.2.4.1 Lix*CuyMo6Ss Lix*Cu,Mo6Sex LiX*I,Mo6Sex-, Lix*In2-,Mo6Se6 LixMn204 LixMnz04 structure/synthesis: 3.10.3.2.2.3 LixMoS2 LixMoSz exfoliation: 3.1 1.6.1.7 from BuLi reaction with MoSz: 3.11.5.2 intercalation compounds by flocculation: 3.11.6.1.7 preparation of new: 3.11.6.1.7 starting material for: 3.11.6.1.7 Li,Mo+,Ru,Ses Lix[Mo~,Ru,Ses] formation by electrointercalation: 3.11.6.4.2 Lix0jW Li,WO3 structure: 3.10.3.3.1 Lix04Ti2 LixTi204 structurelsynthesis: 3.10.3.2.2.3 Lix04V2 LixV204 structurelsynthesis: 3.10.3.2.2.3 LixS2Ta Li,TaSz lithium deintercalation by hydrolysis: 3.11.6.1.5 Li,S2Ti Li,TiSz coordination of lithium: 3.1 1.6.1.1 from BuLi reaction with Ti%: 3.1 1.5.2 lithium ion ordering: 3.11.6.1.1 LiXS2W LixS2W synthesis of 3.1 1.5.2 LixS2W LixWS2 from LiBH4 melt and WSz: 3.1 1.7.2 Ln*BazCu307 Ln*C 17H32N301x Ln*CzoHz4C13018 Ln *CZOHZ~N~OI s
Ln*CzoH3&13N30 18 Ln*Cz8H4oC130zz Ln*C130iz Ln*HlzN3015 LnS LnS formation: 3.8.3.1.1 L ~ T ~ J - ~ LnTe3-, from reactions using LnC13: 3.1 1.7.2 Lnz*Ca04 Ln20rSr SrLnz04 structure: 3.10.3.3.3 Ln~SzSei+~ LnZSz(SeSey) from lanthanum sesquiselenides: 3.1 1.4.2 LntS3 LnzS3 formation: 3.8.3.1.1 reactions of 3.1 1.4.2 Ln&Sey LnzSdSSe,) from lanthanum sesquiselenides: 3.1 1.4.2 LnzS4 LnzS4 formation: 3.8.3.1.1 Ln2x07-xZr~-x Zr~-~Ln-z~07-~ nonstoichiornetric pyrochlore: 3.10.2.3.4 LnX03W LnxW03 structure: 3.10.3.3.1 Lu Lu reaction with 0 2 : 3.8.2.1.1 LUO LUO formation: 3.8.2.1.1 LW03 Luzo3 formation: 3.8.2.1.1 M M*CisH3oN3% M*Cso.sSz M*Fe204 M*H4N05Ti M*Lio.sSz MxKiI"I'3 MxK4Te3 from reactions of MTe and Te in KzS melts: 3.1 1.7.2 Mg*Alz04 Mg*Cz4H36Nizss
Compound Index
437
structure: 3.10.3.3.3 MnO MnO formation: 3.8.2.1.1 homogeneity range: 3.10.1.5.2 MnO1.oo-i.18 MnOl.00-1. I S formation, structure: 3.10.2.2.1 MnOz MnOz formation: 3.8.2.1.1 formation from Mn oxidation: 3.8.2.9.2 hollandite: 3. 10.1.3.2 MnO2 a-Mn02 structure: 3.10.3.3.3 MnO2 LMn02 structure: 3.10.3.3.3 MnPS3 MnPS3 intercalation by ion exchange: of host metal atoms: 3.1 1.6.2 MnS MnS synthesis of 3.8.3.6.1 MnS a-MnS formation: 3.8.3.1.1 MnSz MnS2 formation: 3.8.3.1.1 MnS132[Mn@6)(Ss)12synthesis of 3.8.3.6.2 MnSe82[Mn(Se4)212formation: 3.8.4 MII~*C~B~'~O~Mn2*C606S42Mn2*C606Se82Mnz*CsH16Ss2Mnz*CioOlo Mnz*CzoHloOsSz Mnz*Cz4H1506S3 Mnz*Cz4H3004Te4 Mnz*C3oH6006P4Tez Mnz*C7zH116s4 Mn2*Li0GX Mn2*LixO4 MnzN1003o Mnz(NO3)io formation from MnZ(C0)lo: 3.8.2.8.3 MnrO3 Mn203
438
Compound Index formation: 3.8.2.1.1 Mo02S22[MoSZOZ~Zsynthesis of 3.8.3.6.1 MOO3 Moo3 crystallographic shear in: 3.10.1.3.1 formation: 3.8.2.1.1 formation from Mo and H202: 3.8.2.3.1 homologous series: 3.10.1.2.2 reaction with KzSe4: 3.8.4 reaction with NbzO5: 3.10.3.1.3 reduction of 3.10.1.5.3 structure: 3.10.3.2.4.2 structure: 3.10.3.2.4.3 Mo03Rbo.3 RbosMoO3 structure: 3.10.3.2.4.3 M003Rbo.33 Rbo.33M003 structurelsynthesis: 3.10.3.2.4.3 MoO3Tl0.3 Tlo.sMoO3 structurelsynthesis: 3.10.3.2.4.3 M003T10.33 Tl0.33Mo03 structurelsynthesis: 3.10.3.2.4.3 M0042MOO$formation from MOC140: 3.8.2.9.1 Moo& (M004)2formation from Mo: 3.8.2.9.2 M0045W14 MOW14045 structure: 3.10.3.3.1 MoSSe42[MoS(Sed)]Zformation: 3.8.4 MoS2 MoSz formation: 3.8.3.1.1 synthesis o f 3.8.3.6.1 tetrachloroethylene, 1-hexene by fluocculation: 3.1 1.6.1.7 MoSz Mo&( 1T) formation by deintercalation: 3.1 1.6 formation by deintercalation of K,MoSz: 3.11.6.1.1 metastable phase: 3.1 1.6 MoSz MoSz(2H) alkali metal intercalation compounds: 3.1 1.6.1.1 intercalation of molecules by
439
440
Compound Index Mo6*In2-,LiXSe6 MO6*In2Se6 MO6*In2Te6 Mo6*G.9017 MO6*K6Se27 Mo6*Lio.9017 MO6*Li2Se6 MosNao.9017
NW9Mo6017 structure/synthesis: 3.10.3.2.4.3 Moo& Ni2Mo6Ss deintercalation: 3.1 1.6 MO6017T1
TlM06017 structure/synthesis: 3.10.3.2.4.3 Mo&8 Moss8 formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 reactions with copper chloride: 3.1 1.7.2 M07*C~2022 M07*Hz4N6024 M070246-
iM0702416precursor to MoS$-: 3.8.3.6.1 MOS023
MO8023 crystallographic shear in: 3.10.3.1.2 MOg0264-
[MO@z6l4reactivity toward (Me3Si)zS: 3.8.3.6.1 Mog*KsSe40 M0gO26
MO9026 crystallographic shear in: 3.10.3.1.2 M01003iSb2 SbzMo1 0 0 3I
structure/synthesis: 3.10.3.3.5.2 MO I 2* KI2Se5.5 MOI~*I~-~SSI~ Mol5*In-3S 19 Mo15*In2Sels MoisSi9
MoisS19 formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 MoisSe19
MolsSe19 formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 MozoOa4U UM020$ structure: 3.10.3.3.1 M0n*Ban-103n+l2-
Compound Index M0n*Bin-103n+12M O*Can~ 103n+ 12Mo~*CSZO~~+I MonNan-103n+12[N~~-IMO~O~~+II~ structure: 3.10.3.2.1 M0nO3n-1 M0n03n-1 structure: 3.10.3.2.4.4 Mo,SzTal-, Tal-xMoxS:! pyridine intercalation: 3.1 1.6.1.6
44 1
N*C26H2704Ti N*C~OH~~AUS~ N*C~~H~OCI~P~R~ N*C36H3003RhS N*C3gH33C13PzRe N*C39H36PzRhSz N*C54H450P3Rh N*CIO N*CsO3 N*F02 N*H3+xSzTa N*H3CuMo& N*H4AuS3 N*H4CuS4 N*H4M05Ti N*H5S N*HgO3 "a03 NaN03 reaction with XeF6: 3.9.2 reaction with XeOF4: 3.9.2 NO NO formation from (Ag, Zu, Hg) and " 2 0 4 : 3.7.2.6.1 NOZn Zn(NO3)z formation from zinc and N204: 3.7.2.6.2 NOz NO2 formation of oxides of Zn, Cu, Ag, Hg: 3.7.2.6.1 reaction with Pt and Ir complexes: 3.8.2.8.3 NOsU tU02NO3I formation from N204. CH~COOCHZCH~ and U: 3.8.2.8.3 NOsV tVOzN031 formation from Nz04, CH3COOCHzCH3 and V 3.8.2.8.3 NO.~*CZSH~.S+XS~T~ Nz*BaCisH3606 N~*CH~AUS+ N~*CH~CU~S+ Nz*CH4S N2*CU06 N~*C~AUKS~ N~*C~AUS~N~*C~COS~ N2*CzHdChHgSe2 Nz*CzH7BrHgSe Nz*CzH7CIHg04Se Nz*CzH7CIHgSe
442
ComDound Index
Compound Index
443
444
Compound Index Na*Ca7Nb5017 Na*Ca24Nbz5087 Na*CI Na*CrS2 Na*CrsSes Na*CuFeS2 Na*F Na*FeH402Sz Na*Fe07P2 Na*HS Na*H4B Na*Mn02 Na*N03 Na04ScTi NaScTi04 structure: 3.10.3.3.3 Nao.lsNb~S4 Nao.I 8Nb3S4 reaction of Nb& with Na: 3.1 1.7.2 Nao.zo*MnOz Nao.33*Hzy0,SzTa Nao.33Mo03 NN.33Mo03 structure/synthesis: 3.10.3.2.4.3 Nao.33S2Ta NaoxTaSz from NazSzOdI’aSZ reaction: 3.1 1.5.1 reactions of: 3.1 1.5.2 Nao.wCrl.lsSe2 Nao.34Crl.lsSez cation distribution: 3.1 1.6.1.1 Nao,40*MnOz Nao.44*MnOz Nao.56*Feo.z804Ti1.72 Nao.sStTi Nao~TiSz synthesis of 3.1 1.7.2 Naz*C2H& Naz*C4NzS2 Na2*C7H& Na2*Cr04 Naz*H4Mn04 Naz*Ir04 NazO4Pd Naz0. Pd03 formation from Pd: 3.8.2.9.2 Na204Pt Na2O PtO3 formation from Pt: 3.8.2.9.2 NazO4Ru Na20 RuO3 formation from Ru: 3.8.2.9.2 Naz04Sz NazS204 reducing agent: 3.1 1.6.1.5
Compound Index Na~04U Na2U04 oxides with anion chains: 3.10.3.4.3 Na207Tis NazTi307 structure: 3.10.3.3.2 structurelsynthesis: 10.3.2.4.6 Naz07Uz NazUz07 oxide containing UO6 octahedra: 3.10.3.4.3 Naz019Ti9 Na2Tig01g structure: 3.10.3.3.2 NaZS Na2S equilibrium in water with NaSH: 3.8.3.6.1 melting point of 3.8.3.6.2 reaction o f 3.7.3.6 NazS3 NazS3 melting point of 3.8.3.6.2 NazS3Se3 NazS3Se3 synthesis of 3.1 1.5.2 Na2Se2 NazSez formation: 3.8.4 NazSes Na2Ses reaction of 3.8.4 NazTe2 Na2Te2 formation: 3.8.4 NasXO9Rer Na3,Re409 structure: 3.10.3.3.3 Na3*Fe2S4 Nq*Mn40 18Ti5 N~Nbs03sPs N&"%P603s structurehynthesis: 3.10.3.3.5.2 Nq*O&e NWOZ4U7 Na6U7024 oxide containing U06 octahedra: 3.10.3.4.3 Nan-1*M~n03n+12Nan-~Nbno~n+P "an-1 Nbn03n+1I" structure: 3.10.3.2.1 Nan-iO~ntiTanZ"an-1Tan03nt11" structure: 3.10.3.2.1
N~,,-103~+1Ti~Z"an-iTinO3n+ i I" structure: 3.10.3.2.1 Nan-l03n+lVn2"an-1Vn03nt11structure: 3.10.3.2.1 Nan-l03n+lWnZ"an-1Wn03n+lIm structure: 3.10.3.2.1 NaxOzTi NaxTi02 structurelsynthesis: 3.10.3.3.2 Na,SzTa NaxTaS2 reaction of TaS2 and Na in liquid NH3: 3.11.5.2 NaxSzTi NaxTiS;, coordination of sodium: 3.1 1.6.1.I homogeneity ranges o f 3.1 1.6.1.1 reaction of TiS2 and Na in liquid NH3: 3.11.5.2 sodium ion ordering: 3.1 1.6.1.1 Nb Nb reaction with 0 2 : 3.8.2.1.1 Nb*AgxS2 Nb*BaS3 Nb*C4HgS& Nb*C4H12C1303Sz Nb*C6H1&Nb*CsH I 8Lio6 Nb*CsHl&Nb*CloHloC12 Nb*CloHz4C13N403 Nb*CisH3sOs Nb*C16H3&Nb*CdboN4 Nb*C17HlsSe2 Nb*CigHz50s Nb*C20H450 N~*C~~H~OAS~CI~O~ Nb*C36H3oC1303Pz Nb*C130 Nb*CI3S Nb*Cls Nb*Cr,St Nb*Cs07Ti2 Nb*Cuo.66Sz Nb*F2Se Nb*F3Se Nb*F4Se Nb*HOsTi Nb*HOsTi
445
446
Compound Index
Nb*Lil-,03-2, Nb*Mn,S2 Nb,*Na,-l O3,+12NbnO~n+lPbn-12[Pbn-1 Nbn03n+1I" structure: 3.10.3.2.1 NbO NbO formation: 3.8.2.1.1 homogeneity range: 3.10.1.5.1 Nb00.982-1.008 Nb00.982-1.008 formation, structure: 3.10.2.2.1 NbOz Nb02 crystallographic shear in: 3.10.3.1.1 formation: 3.8.2.1.1 NbS2 NbS2 intercalation compounds of the transition metals Fe, Co, Ni, Ti, V, Cr, Mn: 3.11.6.1.3 metallocene intercalation: 3.1 1.6.1.7 synthesis of 3.8.3.6.1 NbS2 NbSz(2H) ammonia intercalation: 3.1 1.6.1.6 NbS2 Nbl+xS~ formation: 3.8.3.1.1 NbS3 NbS3 formation: 3.8.3.1.2 lithium intercalation: 3.1 1.6.3 NbS& [NbS4]3synthesis of 3.8.3.6.1 NbSe2 NbSe2 intercalation compounds of the transition metals Fe, Co, Ni, Ti, V, Cr, Mn, Rh: 3.1 1.6.1.3 metallocene intercalation: 3.1 1.6.1.7 NbSe3 NbSe3 lithium intercalation: 3.1 1.6.3 NbTez NbTe2 lithium intercalation of: 3.1 1.6.1.1 sodium intercalatio of 3.11.6.1.1 NbTeld[NbTe 1013formation: 3.8.4 Nbi.&z Nb1.6Sz
from reaction of H2S and the metal oxide: 3.11.4.2 from reaction of H2S with Nb: 3.1 1.4 Nbl+x*CU0.66S2 Nb,*B aO3Ti I-, Nb2*CCoXS2 Nb2*CCrXS2 N~~*CCUO.~S~ Nb2*CCuxS2 Nb2*CFexS2 Nb2*CMnxS2 Nb2*CNixS2 Nb2*CS2 Nb2*CS2Vx Nbz*CzoH20MoS4 N~~*C~SH~OB~~N~SIO Nb2*Ca207 NbOs Nb20s crystallographic shear in: 3.10.1.3.1 crystallographic shear in: 3.10.3.1.3 crystallographic shear in: 3.10.1.4.2 formation: 3.8.2.1.1 reaction with WO3: 3.10.3.1.2 reduction of 3.10.1.5.3 structure: 3.10.3.3.2 structure at high pressure: 3.10.3.4.2 Nb209Ti2 Ti2Nb209 structure: 3.10.3.3.2 Nbz017Zr6 NbzZr6O 1 7 structure of composition: 3.10.3.4.1 Nb2021Zrs NbzZrsOz 1 'locked' in structure: 3.10.3.4.1 N b3*KO 15P3 Nb3K0.18S4 Ko.1sNb3S4 reaction of Nb& with K: 3.1 1.7.2 W*NW.I& Nb3S4 Nb3S4 electrointercalation (alkali metals): 3.1 1.6.4.1 thermal intercalation (In, Cu Ag, Zn, Cd): 3.1 1.6.4.1 Nb~Se4 Se4*Nb3 electrointercalation (alkali metals): 3.1 1.6.4.1 thermal intercalation (In, Cu Ag, Zn, Cd): 3.11.6.4.1 Nb~Te4 Nb3Te4
Compound Index electrointercalation (alkali metals): 3.1 1.6.4.1 thermal intercalation (In, Cu Ag, Zn, Cd): 3.11.6.4.1 Nb4.9zS4Ta6.08 Nb4.9zS4Ta6.08 synthesis in high frequency furnaces: 3.11.7.1 Nb4*Fe~K2013 Nb4*KzMgzOi3 Nb4*KsSe22 Nb403iW7 Nb4W7031 coherent intergrowth: 3.10.1.4.1 Nbs*CazO15T1 Nbs*Ca7Na017 N~~*C&I.~+XC~ZOZ~ Nb60198“b601918formation from Nb: 3.8.2.9.2 formation from NbC15: 3.8.2.9.1 NbgSi75“b6S 1715synthesis of 3.8.3.6.1 Nbs*NdkPs Nbs047W9 NbaW9047 coherent intergrowth: 3.10.1.4.1 Nbl1*Ge029 NbiiOd’ PNb I I 0 2 9 crystallographic shear in: 3.10.3.1.3 NbizOz9 Nb12029 oxidation and structure: 3.10.3.1.3 Nbiz033W WNbiz033 coherent intergrowth of 3.10.1.5.4 crystallographic shear in: 3.10.3.1.3 N~M*B&I.~~K~.I~~OP~ Nbi40uW3 W3Nb1 4 0 4 4 coherent intergrowth of 3.10.1.5.4 N b I 4+x * K7060P9-~ Nbi6094Wi8 Nbi 6W 18094 structure: 3.10.3.3.1 Nb24 * 062Ti Nb~s*Caz4NaOa7 Nbz6077W.1 W4Nbz6077 coherent intergrowth of 3.10.1.5.4 Nb3i*F077 Nd Nd
reaction with 0 2 : 3.8.2.1.1 Nd*C~HzoN3014 NdO
447
448
Compound Index
Ni*C38H& Ni*C3gH3&jOP2 Ni*C4oH72N& N~*C~~H~~AS~CIZOI~ Ni*C52H52C12012P4 Ni*C54HggP3 N~*C~~H~OAS~C~Z~I~ N ~ * C ~ ~ HI 2P4 ~OC~Z~ Ni*C12 Ni*C12 Ni*C1208 Ni*F4K2 Ni*Fe204 Ni*Mo2S$NiN202 Ni(Nz)(02) matrix isolation: 3.8.2.1 1.3 NiN402 Ni(Ndz(02) matrix isolation: 3.8.2.1 1.3 Ni*N40 I 2 NiO NiO defect structures: 3.10.1.1.1 formation: 3.8.2.1.1 formation from Ni oxidation: 3.8.2.9.2 homogeneity range: 3.10.1.5.1 homogeneity range: 3.10.1.5.2 NiOl.mi.ooi NiOl.oocrmi formation, structure: 3.10.2.2.1 Ni02 Ni(O2) matrix isolation: 3.8.2.1 1.3 Ni04 Ni(02)2 matrix isolation: 3.8.2.1 1.3 NiPSj NiPS3 redox intercalation: 3.1 1.6.2 NiS NiS synthesis of: 3.8.3.6.1 NB B-NiS formation: 3.8.3.1.1 NiS2 NiS2 formation: 3.8.3.2.1 NiSs2“i(Sd212synthesis of 3.8.3.6.2 NiSeg[Ni(Se4)]2reaction of 3.8.4
Compound Index
449
Compound Index
450 O*HF5Te O*H2 O*H2C15Ru O*H~~CIN~RLI O*Hi&ONs O*H~~N~RU~+ O*Hg O*Ho
O*KH
O*Liz O*Lu O*Mg O*Mn O*MOS32O*MoSe$ O*MoTe$O*Mo3S$O*N O*NZn O*Nb O*Nd O*Ni OPd PdO formation: 3.8.2.1.1 O h PmO formation: 3.8.2.1.1 O h
Pro
formation: 3.8.2.1.1
OPt PtO formation: 3.8.2.1.1 OSesW2[W(O)(Se4)212formation: 3.8.4 OSm SmO formation: 3.8.2.1.1 OSr SeO non-stoichiometric oxide: 3.10.2.1 OTb TbO formation: 3.8.2.1.1 OTesWz[W(O)(Te4)z12formation: 3.8.4
OTi Ti0 homogeneity range: 3.10.1.5.2 metallic conduction: 3.10.1.1.1 OTm TmO
formation: 3.8.2.1.1
ov vo
homogeneity range: 3.10.1.5.2 OYb YbO formation: 3.8.2.1.1 OZn ZnO cation vacancy defects: 3.10.1.1.2 formation: 3.7.2.1.1 formation from Zn and (NO2 or COz): 3.7.2.6.1 formation from zinc dialkyls and SOz: 3.7.2.6.2 formation from Zn and Na202: 3.7.2.7.2 formation from Zn and steam at dull red heat: 3.7.2.2.1 homogeneity range: 3.10.1.5.2 non-stoichiometric oxide: 3.10.2.1
ozu
zuo
formation from Zn and H202: 3.7.2.3.1 ~0.5oooO.50-16*~~ 00.65-1.25Ti
TiOo.65--1.25 formation, structure: 3.10.2.2.1 00.80-1Jov
VoO.80-1.3O
formation, structure: 3.10.2.2.1 O0.982-l.I308*Nb 01.w.I8*Mn 01.000-1.001 *Ni 01.000-1 .0l2*CO 01.~5-1.2co*Fe 01.~0-1.7o*Ce 0130-1.7Oh ~1.50--1.70
formation, structure: 3.10.2.2.2 01.72-2.00*Ce 01.72-2.ooPr MI .72-2.O0
formation, structure: 3.10.2.2.2
0 2 0 2
formation of adducts: 3.8.2.1.2 insertion into group IB and IIB metalligand bonds: 3.7.2.1.3 insertion into transition metal-ligand bonds: 3.8.2.1.3 reaction with CuC1: 3.7.2.1.2 reaction with Cd(Et)z: 3.7.2.1.2 reaction with IB and IIB metals: 3.7.2.1.1
Compound Index
451
452 02*FloSe2Xe Oz*FloTez Oz*FloTezXe 02*FloW2Xe Oz*Fe 0z*FeH4NaS2 OZ*Ge Oz*HFzP 0z*H2 Oz*HzC14MoOz*HzF4Te4 Oz*HzHg OZ*H~~N~RU Oz*H3oCo2Nio+3 0z*Hf 02*Ir Oz*%SesVz Oz*&SeloVz 02*LiMn OzLiosTi Li0,~TiOz structure/synthesis: 3.10.3.3.2 0z*Mn OZ*MnNa Oz*MnNao.zo Oz*MnNao.40 Oz*MnNao.u Oz*Mo 02*MoS22Oz*MozS$ 0z*N 0 2 * Na,Ti 02*Nb 02*Ni OZ*NiNz 02*NiN4 020s
oso:!
formation: 3.8.2.1.1 structure: 3.10.3.2.4.1 O2Pb PbOz bivariant phase oxide: 3.10.2.1 02Pd Pd(0z) matrix isolation: 3.8.2.1 1.3
om
pro2 homogeneity range: 3.10.1.5.2 O2Pt
Ptoz
formation: 3.8.2.1 . I O2Pt Pt(02) matrix isolation: 3.8.2.1 1.3
Compound Index OzRe Re02 formation: 3.8.2.1.1 formation from ReCl5 disproportionation: 3.8.2.9.1 02Rh WOz) matrix isolation: 3.8.2.1 1.3 02Rh RhOz formation: 3.8.2.1.1 02Ru RuOz structure: 3.10.3.2.4.1 formation: 3.8.2.1.1 02s
so2
dissolution of metal disulfates: 3.8.2.8.3 formation of crystalline solvates of Cu, Zn, Cd: 3.7.2.6.1 formation of oxohalides and SOX2 (X=F, Br, C1): 3.8.2.8.1 insertion into transition metals: 3.8.2.8.2 O2Se SeOz use in formation of selenides: 3.7.4.4.1 Oz*Se2Ozz-Se Se032reaction of 3.8.4 OzSi SiOz phase formation: 3.10.3.4.2 reaction with xenon fluorides and oxyfluorides: 3.9.2 02Sn SnOz crystallographic shear in: 3.10.3.1.1 02Ta TaOz formation: 3.8.2.1.1 O~TC TcO2 formation: 3.8.2.1.1 02Te TeO;! reaction of: 3.8.4 use in formation of tellurides: 3.7.4.4.1 02Ti Ti02 crystallographic shear in: 3.10.1.3.1
Compound Index crystallographic shear in: 3.10.1.4.2 crystallographic shear in: 3.10.3.1.1 formation: 3.8.2.1.1 formation of solid solutions: 3.10.1.5.5 hollandite: 3.10.1.3.2 oxygen atom elimination from: 3.10.1.2.3 reaction with Ga2O3: 3.10.1.3.3 reduction of 3.10.1.5.3 structure: 3.10.3.2.4.4 substitutions in spinels: 3.10.2.3.5
02u
uo2
homogeneity range: 3.10.1 S.2
02v
vo2
crystallographic shear in: 3.10.1.3.1 crystallographic shear in: 3.10.1.4.2 crystallographic shear in: 3.10.3.1.1 formation: 3.8.2.1.1 reduction of 3.10.1.5.3 structure: 3.10.3.2.4.1
02w w02
formation: 3.8.2.1.1 02Zr zfl2
fluorite structure: 3.10.2.3.3 formation: 3.8.2.1.1 formation of solid solutions: 3.10.1 S . 5 superstructure movement: 3.10.3.4.2
02.00-2.24u
uo2.OC-2.24
formation, structure: 3.10.2.2.3
0 3 03
oxidation of alkaline Xe(V1) solutions: 3.9.2 reaction with Ag: 3.7.2.1.1 03*AgN 03*A12 O3*AsFgSXe2 O3*AU2 03*BF15Te3 0 3 *Bal -,La,Ti O3*Ba2 O3*BaNbxTi1-, O3*BaNi O3*BaTi O3*Bi2 0 3 83Br
453
454
Compound Index 03*H02 03*Irz 03*K0.33Mo 03*K0.3Mo O3Kr GO3 non-existence: 9.3.4 O3*La2 O3*Lio.33Mo 03*Li,W 03*LnxW 03*LU2 O3*Mn2 03*MO 03*MoRbo,3 03*MoRbo.33 03*MOTlo.3 03*MoTlo,33 03*NNa 03*
[email protected] O3*Nd2 0 3 h Z
PmzO3 formation: 3.8.2.1.1 O3Re Re03 formation: 3.8.2.1.1 metallic conduction: 3.10.1.1.1 structure: 3.10.3.2.1 structure: 3.10.3.2.4.4 structural type in oxyfluorides: 3.10.3.4.3 03mZ
Rho3 formation: 3.8.2.1.1 formation from Rh oxidation: 3.8.2.9.2 O3Rn RnO3 possible formation from hydrolysis of RnF4 or RnF6: 9.3.4 0&Ti S2Ti03 defects in ternary oxides: 3.10.1.2.2 03SC2 SC203 formation: 3.8.2.1.1 OsSeZn ZnSe03 intermediate in formation of ZnSe: 3.7.4.4.2 O3Sm SmzO3 formation: 3.8.2.1.1 O3SrTi SrTiO3 as discrete compounds: 3.10.1.5.4
Compound index intergrowth to form homologous series: 3.10.1.5.4
planar boundaries in: 3.10.1.3.3 structure: 3.10.3.2.1 .I O3TC TCO3 formation: 3.8.2.1.1 03TeZn ZnTeO3 formation: 3.7.4.4.2 03Ti2 Ti203 formation: 3.8.2.1.1 homogeneity range: 3.10.1.5.1 03Th TI203 bivariant phase oxide: 3.10.2.1 03Tmz Tm203 formation: 3.8.2.1.1 03u
uo3
reaction with
u308:
3.10.3.4.3
03VZ
v203
formation: 3.8.2.1.1
03w
wo3
crystallographic shear in: 3.10.1.3.1 crystallographic shear in: 3.10.1.4.2 formation: 3.8.2.1.1 formation of solid solutions: 3.10.1.5.5 formation from W and H202: 3.8.2.3.1 oxygen atom elimination: 3.10.1.2.3 phase formation: 3.10.3.4.2 reduction according to structure: 3.10.1.2.1 reduction of 3.10.1.2.2 reduction of: 3.10.1.5.3 superstructure movement: 3.10.3.4.2 tungsten bronzes: 3.10.1.3.2 03Xe XeO3 formation: 3.9.2 reaction with aqueous base: 3.9.2 reaction with ozone: 3.9.2 03y2 y203
formation: 3.8.2.1.1 O3Ybz Yb203 formation: 3.8.2.1.1 03+,*LaMn 03-~.5~*BaTai-~ O3-zX*Lil-,Nb 03-,*CaFe
03-,*CaMn 03-x*FxM0 O3-x*FxW 03n+1*Ban-IMon203,,+1 *Bin-lMo$ 03n+1 *Can-IMon203n+l*CS2MOn 03n+1*Kn-lTin203n+l*Kn-lVn203n+1*MonNan-1203n+i*Nan-i Nbnz03n+l*Nan-1Tan203n+1*Nan-1Tin2%+I *Nan-IVn203n+1*Nan-1Wn20 3 n + 1 *NbnPbn-1203n+iSrn-iTan2[Srn-iTan03n+ilm structure: 3.10.3.2.1 Oin+iSrn+iTin Srn+1Tin03n+1 structure: 3.10.3.2.1.1
0311-1 *Man 03n-1Wn
WnO3n-I structure: 3.10.3.2.4.4 04*Ag 04*AgzS 04*AgzSe 04*Ag2Te 04*AlCI 04*AIGeNa 04*A12Mg 04*Au 04*BaU 04*BaXCuLa2-, 04*C2Au 04*C2CU 04*C2H7ClHgN2Se 04*C2Ti 04*C4C12Rh2 04*C4cO 04*C&oF6 04*C4CrTe$04*C&Mn 04*C&Ni 04*C4Fd(e 04*C4Fe204*C4H4AuNaS 04*C&Co 04*C4H6Hg 04*C&S 04*C&,Zn 04*C4HioCd O~*C~HIOF~ZN~S~
455
Compound Index 04*Fe212N4 04*Fe2M 04*Fe2N4S2204*Fe2Ni 04*Fe2Sr 04*Fe3 04*Fe4N4 04*HCI 04*HRe 04*H2S 04*HzSe 04*H2Te 04*H4AgO~*H~AU O~*H~AU04*H4Na2Mn 04*HsZn 04*IrNa2 04*KzMO 04*LiFeSn 04LiTi2 LiTi20.1 structure/synthesis: 3.10.3.3.2 04*LixMn2 04*LixTi2 04*LixV2 04*Ln2Sr 04*MgA12 04*MgS~2 04*MO 04*M0204*Mn3 04*N2 0 4 * NazPd 04*Na~Pt 04*NazRu 04*Na2S2 04*NazU 04*NaScTi 04*Ni 040s
Os04 formation: 3.8.2.1.1 formation from 0 s oxidation: 3.8.2.9.2 04Pd Pd(O2)z matrix isolation: 3.8.2.1 1.3 04Pt R(02)2 matrix isolation: 3.8.2.11.3 04*RbxB~ 04Re[Re041reactivity toward polysulfido anions: 3.8.3.6.2
457
04Reformation from ReCl5 disproportionation: 3.8.2.9.1 04Rh Rh(0212 matrix isolation: 3.8.2.1 1.3 04Ru RUo4 formation: 3.8.2.1.1 04SczSr SrSc204 structure: 3.10.3.3.3 O4SeZn ZnSe04 formation: 3.74.4.2 04Sr2Ti Sr2Ti04 electron optical examination of 3.10.1 S.4 intergrowth to form homologous series: 3.10.1 S.4 structure: 3.10.3.2.1.1 04SrU SrU04 rutile type structure: 3.10.3.4.3 OdCtTc041reactivity with thiolates: 3.8.3.6.3 04TeZn ZnTe04 formation: 3.7.4.4.2 Oqv3vo43-
formation from Vc14: 3.8.2.9.1
04w2-
WO412precursor to MOS42-: 3.8.3.6.1 04w2wo42-
formation from W: 3.8.2.9.2 04Xe Xe04 formation: 3.9.2 04-,*LiMnz 05*AlCa2Fe 0 5 *BazCuT1 05*CsBrMn 05*C5BrRe Os*C5ClMn 05*C5CIRe 05*C5Fe 05*C5HMnS 05*C5HSW 05*c5n2sw05*C5H I &I3 W
458
Compound Index
460
-
Compound Index
07*NazTi3 07*NazUz O7NzTi TiO(N03)z formation from Ti and N204: 3.8.2.8.1 O7Rez Re207 formation: 3.8.2.1.1 07Sr3Tiz Sr3Tiz07 as discrete compounds: 3.10.1.5.4 structure: 3.10.3.2.1.1 07Tb4 Tb& formation: 3.8.2.1.1 07TCz TCz07 formation: 3.8.2.1.1 07Tb Ti407 formation: 3.8.2.1.1 homologous series: 3.10.1.2.2 07v4 v407
crystallographic shear in: 3.10.1.4.2 07-x*LnzxZrz-x 08*BazCaCu~T12 08*BazCazCu3Hg Os*C4FizXe Os*CsHioMozNzSz Os*CsCoz 08*CsFeSezWZ+ 08*CsHzMozSZOs*CsHizMoz Os*C 1zH 18FizPzPd O~*CIZHZOAU~N~N~ZS~~Os*Ci4HzoAgN O8*Ci6H36C1izSbzZn Os*Ci6H36RhzP2Sz Os*CzoH4Fz4Hf Os*CzoH4Fz4Zr Os*CzoHloMnzSz Os*CznHioRezSz Os*CzoHzsHf Oa*CzoHzsTh Os*CzoHz8Zr Os*CzoH3oV O~*C~~H~CI~ZCUS~Z Os*CdCIz 08*ClzCO 08*CIzCu O8*CIzFe Os*CIzHg Os*ClZMn Os*CIzNi
Os*ClzZn Os*CuRez Os*FeLi3Sbz Os*GaTi Os*Li 1+xV3 08u3 u308
reaction with uo3: 3.10.3.4.3 superstructure: 3.10.3.4.2 09*AuzSe3 09*BaTi4 09*BazCa~Cu3TI 09*C3BFgS3 Og*CgFe3Tez 09*C9HFe3S 09*CisH36AgF3NzS 09*C~oH34AuPS 09*Cz7H63NaZrz 09*C4oHs4IrNzP3 0g*C~N30g*H 18C14M03PdS4 O~*H~~CI~MO~S~ 09*H 18M03S44+ oy*LaN3
09*N3Sm Og*Na3-xRe4 09*NbzTiz 09TbTIz TIzTi409 structure/synthesis: 10.3.2.4.6 09Tis
t1509
crystallographic shear in: 3.10.3.1.1
09u4 u409
formation, structure: 3.10.2.2.3 09VS v509
crystallographic shear in: 3.10.1.4.2 Olo*Ba~Ca2Cu3T12 Olo*BazCa3Cu.+Hg O~O*B~~C~~CU~S~Z Oio*CsHi6NzU Olo*CloMnz 0I O * C ~ O H S ~ I ~ N Z P ~ Olo*CwH86Taz OlO*KZW3 01OSr4Th Sr4Ti3010 homologous series: 3.10.1.5.4 structure: 3.10.3.2.1.1 01l*BazCa3Cu4TI O11*M04 Ollfi6 fi6011
Compound Index
461
462
Compound Index
Compound Index 094*Nb16Wia 011z*Ce62 0 112pr62
Pr620112 formation, structure: 3.10.2.2.2 OllZTb62
0112Tb62 formation, structure: 3.10.2.2.2 OlaoPrss
0160Pr88 formation, structure: 3.10.2.2.2 OY*Cao.5FeH2,Sz Oy*HzyKxPt4S6 OY*HzyNao.33S~Ta 0s 05
reaction with 0 2 : 3.8.2.1.1 Os*C55H&lOP3 OS*C$~H~Y~ZP~ OS*HZO~Z-
os*oz 05*04 OSSZ
0552
formation: 3.8.3.1.1
463
464
Compound Index
466 Pbn-1 *Nbn03nt12Pbx*Lio,65S2txV PbxS4+xTa2 (PbS)dTaS2)2 intercalation in: 3.1 1.6.1.4 PbxSa+xTh (PbS)x(TiS2)z intercalation in: 3.1 1.6.1.4 Pd Pd reaction with 0 2 : 3.8.2.1.1 Pd*CarF5 Pd*C6HioS4W Pd*CloHlzBrFsSz Pd*C I ZHIXFI2OxP2 Pd*Ci 2H360 I 2p4 Pd*C I ~ H z o B ~ F ~ S Z Pd*Ci6H3oF604Pr Pd*C3oH~oBrF5Sz Pd*C39H3oF@Pz Pd*C@H72NsS4 Pd*C48H40PzSex Pd*C7zH6oP4 Pd*C12 Pd*HxNzSI I Pd*H 1xC14M0309S4 Pd*KzSelo Pd*Na204 Pd*O Pd*02 Pd*04 PdS PdS formation: 3.8.3.1.1 PdS2 PdS2 formation: 3.8.3.1.1 PdS112[Pd(S5)(C1-S6)12synthesis of 3.8.3.6.2 Pd3*CszS4 Pd3*K2S4 Pd4S Pd4S formation: 3.8.3.1.1 Pm Pm reaction with 0 2 : 3.8.2.1.1 Pm*O Pm2*03 Pr Pr reaction with 0 2 : 3.8.2.1.1 Pr*Ci4HzoN3014 Pr*C18H36C13021 Pr*CzoH4oC13022
Compound Index
Compound Index synthesis o f 3.8.3.6.2 PtS1sZ[Pt(W312synthesis of 3.8.3.6.2 P~~*C~ZH~~P~SZ Pt3*CszS4 Pt4*H2y&O& Ph*K2S6 Pt4*K4Sezz Pt4S6 hs6
formation by deintercalation: 3.1 1.6 metastable phase: 3.1 1.6 PtqS224[ptab3-s)4(s3)6l4synthesis of 3.8.3.6.2 PU*c 18H54C1406P6 Pu*C36H30C1403S3 PU*C14 PU*Cl&2
467
Compound Index s*co S*Cr
s*cu S*CUl.97 s*cuz S*Cuz-,
S*Eu
S*F203Xe S*FtjO&e S*Fe S*Fex S*HF03 S*HNa S*Hz S*Hz04 S*H5N S*HI~N~RUZ+ S*Hfz S*Hg S*Ir S*Li2 S*Ln S*Mn S*MoSe$S*Na2 S*Ni
s*oz
S*O1gTaW53S *Pd S*Pd4 S*Pt
ssc scs
formation: 3.8.3.1.1 SSe4W2[WS(Se4)1*formation: 3.8.4 STi TiS formation: 3.8.3.1.2
sv vs
formation: 3.8.3.1.1
sv3 v3s
formation: 3.8.3.1.1 SZn SZn formation: 3.7.3.1.1 formation: 3.7.3.6 nanoparticle synthesis: 3.1 1.5.1 solubility: 3.7.3.2 S$Zn [zn(S4)212formation: 3.7.3.6
469
470
ComDound index
Compound Index
471
Sz*Re Sz*Ru SzSn SnS2 metallocene intercalation: 3.11.6.1.7 source of S2-: 3.8.3.6.1 S2Ta TaS2 alkali metal intercalation: 3.1 1.6.1.1 formation: 3.8.3.1.2 from reaction of HzS with Ta: 3.1 1.4 intercalation compound of the transition metals Fe, Co, Ni, Ti, V, Cr, Mn, Rh: 3.1 1.6.1.3 metallocene intercalation: 3.11.6.1.7 synthesis o f 3.8.3.6.1 SZTa TaS2( IT) structural transformation to TaSz(2H) induced by intercalation: 3.1 1.6.1.1 S2Ta TaSz(2H) ammonia intercalation: 3.1 1.6.1.6 intercalation: 3.1 1.6.1.7 pyridine intercalation: 3.1 1.6.1.6 structural transformation to TaSz(2H) induced by intercalation: 3.1 1.6.1.1 SzTi TiS2 alkali metal interalation compounds of 3.11.6.1.1 ammonia intercalation: 3.1 1.6.1.6 formation: 3.8.3.1.1 metallocene intercalation: 3.11.6.1.7 synthesis of: 3.8.3.6.1 &Ti TiSz(cubic) formation by deintercalation: 3.1 1.6 formation by deintercalation: 3.1 1.6.4.2 intercalation (lithium): 3.1 1.6.4.2 metastable phase: 3.1 1.6 structural transformation to Ti& (hexagonal): 3.11.6.4.2 SzTi TiSz(hexagona1, layer) formation by structural transformation from TiSz (cubic): 3.11.6.4.2 SzTil+x Til+,Sz self-diffusion of lithium in: 3.1 1.6.1.1
s2v
VSZ formation by deintercalation: 3.1 1.6 metallocene intercalation: 3.1 1.6.1.7 metastable phase: 3.11.6
472
Compound Index S3*FeP S3*Fe4N707 S3*H4AuN S3*Hf S3*Ln2 S3*Ln2SeY S3*MnP S3*MO S3*Na2 S3*NazSe3 S3*Nb &*Nip S3*OMo2S3*PZn S3*Rh2 S3Sb SbzS3 source of S2-: 3.8.3.6.1 SsSr,Ti SrxS3Ti from reactions of H2S with SrCO3L 3.11.4.2 S3Ta TaS3 lithium intercalation: 3.1 1.6.3 S3Ta Tal+,S3 formation: 3.8.3.1.1 S3Ti Ti& formation: 3.8.3.1.1 lithium intercalation: 3.1 1.6.3 SsTi2 TizS.3 formation: 3.8.3.1.2 s3v2
VZs3 formation: 3.8.3.1.1 s3y2 y2s3
formation: 3.8.3.1.1 S3Zr ZrS3 formation: 3.8.3.1.1 lithium intercalation: 3.1 1.6.3 S3,9*CrLal.9 &*Ag62&*Ag7S4*Br4Fe42S~*C~H~CO~S4*C4H9Nb2S~*C~H~~COP~ S4*C6H1oM02N2062s4*C6HioPdW Sd*CsAgN$S4*CsAuN&
474
ComDound Index
Compound Index
475
476
Compound Index
Compound Index
477
SeZ*C18H54HgSi4 Sez*C18H54Si4Zn Se2*C20H54CdSi2 Sez*C20H54HgSi2 Sez*CzoH54Si2Zn Se2*C24H54Br2CdP2 Se2*C24Hs4Br2HgP2 Se2*C24H54CdC12P2 Sez*Cz4H54CdIzPz S~~*CZ~HS~CIZH~PZ Se2*C24H54HgI2P2 S~~*C~~H~OAUF~PZS~ Sez*C36H3oC12PzHgz Se2*C36H&d Se2*C36H&n S~~*C~~H~OO~P~RU+ Sez*C40H3oCd S~~*C~SH~OP~P~ S~~*C~~H~IJP~RU~+ Se2*ClCu Sez*Cr Se2*CrK Sez*Cu Se2*CuxV Sez*FloOz Se2*F1002Xe Se2*H&dNlo Sez*HsHgNlo SeZ*Hf Sez*K2 Se2*Li~ Sez*Nao,34Cr1,1s Se2*Na2 Sez*Nb SezSn
5n5e2
metallocene intercalation: 3.11.6.1.7 SeZTa TaSez intercalation compounds of the transition metals Fe, Co, Ni, Ti, V, Cr, Mn: 3.11.6.1.3 metallocene intercalation: 3.1 1.6.1.7 SezTi TiSe:! intercalation compounds of the transition metals Fe, Co, Ni: 3.11.6.1.3 metallocene intercalation: 3.11.6.1.7 SezV VSez metallocene intercalation: 3.11.6.1.7 SezZr
zr5e2
478
Compound Index
Se2Zr (Continued) intercalation compounds of the transition metals Fe, Co, Ni: 3.11.6.1.3 rnetallocene intercalation: 3.11.6.1.7 Se&r ZrSez-, intercalation of lithium: 3.1 1.6.1.1 Se3*Au209 Se3*Au201z Se3*BrCu Se3*CuI Se3*FeP Se3*Hf Se3*NazS3 Se3*Nb Se3*Sb2 Se3Ta TaSe3 lithium intercalation: 3.1 1.6.3 Se3Ti TiSe3 lithium intercalation: 3.11.6.3 Se3Zr ZrSe3 lithium intercalation: 3.1 1.6.3 Se4*CdCoHgN4 Se4*C5HsMo Se4*C5H5W Se4*C6H12NzZn Se4*C6HzoCdNz Se4*C6Mnz062Se4*CsOsRe22Se4*C8Hz&dN2Zn Se4*CioHzoCuN2 Se4*CioHzoNzZn Se4*C18H36N2Zn Se4*C24H2oAgP Se4*C~H28Tiz Se4*C28HjoAsAuN4 Se4*C32H44AgzW S~~*C~ZH~~AUZW Se4*C32H44CuzW Se4*C3zH~NzCd Se4*C3zH44NzZn Sed*C36H72NsZn Se4*C40HiosAu4 Se4*C4i H39CoP3 Se4*C5zH48IrP4+ S~~*C~ZH~EP~R~ZZ+ Se4*CeK Se4*Kz Seq*MoZSe4*MoSzSe4*Nb3
Compound index
479
480
Compound index
Sr2*04Ti Sr3*06Tiz Sr3*07Tiz Sr3*07Tiz Sr3-x*O~~Ta3 Sr4*01oTi3 Srn-103n+lTan2[Srn-iTan03n+11~ structure: 3.10.3.2.1 Srn+I*%+ 1% Sr,*C~La2-~04 Srx*S3Ti
T THF THF solvent in (Ph3P)2Cu(OOCCH3) formation: 3.7.2.6.3 Ta Ta reaction with 0 2 : 3.8.2.1.1 Ta*Ao.3Sz Ta*AgxSz T~*C~SH~S+~NO,SS~ Ta*C6H&06 Ta*CioHisC14 Ta*CioH1sS$Ta*CloHnN4 Ta*CizH36C13N603P2 Ta*CigH2505 Ta*Cz7H4302 Ta*C36H47N402 Ta*C14Se Ta*C15 Ta*cUO,66sZ Ta*CuxS2 Ta*FzSe Ta*F3Se Ta*F4Se Ta*H2,Nao.33OYSz Ta*H3+xNSz Ta*HxS2 Ta*HgmS2 Ta*Hg& Ta*InS2 Ta*KxS2 Ta*LixS2 Ta*Nao.d% Ta*NaxS2 Ta*O2 Ta*O 1ssw53Ta*OlgW+Ta*S2 Ta*S3 Ta*S43-
Ta*Se2 Ta*Se3 TaTe2 TaTez lithium intercalation of 3.11.6.1.1 sodium intercalation of 3.1 1.6.1.1 Ta1-~*Ba03-2.5~ Tal+x*cUO.66s2 Tal-x*MoxSz Talo.~o*K6030 Ta2*CS2 Ta2*C54H66010 Taz*&Si 1 Ta2*05 Ta~*pb,S4+~ Ta3*CdkS62Ta3*015Sr3-~ Ta4*031W7 T%*Sl+T%,os*Nb4.9zS4 T~i~*Na~-103~+12Tan*Srn-103n+12Tb Tb reaction with 0 2 : 3.8.2.1.1 Tb*O Tb7*012 Tbi i*Ozo Tbl6*030 Tb24*044 Tb48*Oss Tb62*0112 Tc Tc reaction with 0 2 : 3.8.2.1.1 TC*CZ~H~OOS~Tc*Oz Tc*03 Tc*04TC2*07 Te*Ag2 Te*Ag3NO6 Te*AsFlIOXe Te*AuI Te*BrCu Te*CzHsBr2HgIz Te*C3HloSi4 Te*C4Hs Te*C4HgCu T~*C~HIICU Te*C6H&u Te*C6Hi# Te*CsHgO Te*C&I18 Te*C I 2Fe3O 122-
Compound Index Te*C14HzzHg Te*C28H42AuPSi3 Te*Cd Te*CICu Te*Cu Te*CuO3 Te*CuZ Te *F&Xe Te *Fe Te*FloOzSeXe Te*HFsO Te*H2 Te*Hz04 Te*Hg Te*Oz Te*OsZn Te*04Agz Te*04Zn Te*O&ex TeZn ZnTe formation: 3.7.4.1.2 formation: 3.7.4.1.3 formation: 3.7.4.3.1 formation from polychalcogenide: 3.7.4.6.2.1 stoichiometric adjustment: 3.1 1.3.1 Tel-,*GeSe, Tel-,*Re Tez*Au TeZ*AuBr Tez*AuCI Tez*AuI TeZ*BrCu Tez*C6Fe~06 Tez*C6H&dSi8 Tez*C6HlgHgSis Te2*CsHI 8BCu T~z*C~HI~CICU Te~*CgFe30g Tez*CnHlo T~z*CISOISW~ Tez*C16H18Hg02 Te2*CI 8 H d d Tez*C18HzzZn Tez*C18H54CdGezSiz Te~*C1xH&dSi4 Tez*C18H54GezHgSiz Tez*C18H54GezSi2Zn Tez*Cl~H54HgSi4 Te~*C18Hdh4Zn Tez*C I xHs4Si8Zn Tez*CzoCr40~02Tez*CzoH54CdSiz Tez*CzoH54HgSiz
481
482
Compound Index
Compound Index T12*Ba2Cu06 TIz*03 T12*09Ti4 Tlz*O13W4 TI,*CrsSe8 Tl,*S~V6 Tm Tm reaction with 0 2 : 3.8.2.1.1 Tm*O Tm2*03
483
484
486
Compound Index
Compound Index
487
Inorganic Reactions and Methods, Volume6 Edited by J. J. Zuckerman, A. D. Norman Copyright 0 1998 by Wiley-VCH, Inc.
Subject Index This index supplements the compound index and the table of contents by providing access to the text by way of methods, techniques, reaction conditions, properties, effects and other phenomena. Reactions of specific bonds and compound classes are noted when they are not accessed by the heading of the section in which they appear. For multiple entries, additional keywords indicate contexts and thereby avoid the retrieval of information that is irrelevant to the user’s need. Section numbers are used to direct the reader to those positions in the volume where substantial information is to be found. A
Acetamides cointercalated alkali metal compounds 3.1 1.6.1.5 Acetonitrile and I, as oxidizing agent for deintercalation 3.11.6.4.1 as solvent for electrointercalation 3.1 1.6.1.1 Acyloin reactions with 1.2-dithiolenes 3.7.3.5 Adaptive structures and non-stoichiometric oxides 3.10.3.4 infinitely 3.10.3.4 tantulum pentoxides 3.10.3.4.2 Alcohol cointercalated with alkali metal compounds 3.1 1.6.1.5 Alcoholysis dependence on alkyl group 3.8.2.4.2 of dialkyl metal complexes 3.7.2.2.2 of metal ligand bonds 3.7.2.2.2 Alkali halide melts as reaction medium for intercalation reactions 3.11.6.1, 3.11.6.4.2 Alkali metal cations, hydrated 3.11.6.1.5 intercalation compounds of 3.1 1.6.1, 3.11.6.1
melts 3.11.6.3 selenides 3.7.4.6.2.1 tellurides 3.7.4.6.2.1 Alkaline earth cations, hydrated in intercalation 3.11.6.1.5 Alkoxides metal complexes 3.8.2.7.2,3.7.2.7.1 of group IB and IIB metals 3.7.2.1.3 transition metal alkoxides 3.8.2.1.3 Alkylamines intercalation 3.11.6.1.4,3.11.6.1.6 Alkyls reaction of group IB and IIB alkyl complexes with 0 2 and 03 3.7.2.1.3 reaction of transition metal complexes with 0 2 3.8.2.1.3 Alloys indium, intercalation from 3.1 1.6.1.2 Altervalent anions in non-stoichiometric compositions 3.10.3.5 Aluminas beta phases 3.10.3.2 cationic conductivity 3.10.3.2.2.2 Ammine complexes of group IB and IIB metals 3.7.4.4.2
489
490
Subject Index
Amide oxides reactions with transition metal atoms 3.8.1.11.2 Aminothiols of group IB and IIB elements 3.7.3.5.2 Ammonia as solvent in alkali metal intercalation compounds 3.11.6.1.5 intercalation of 3.11.6.1.6 intercalation in layered dichalcogenides 3.11.6.1 liquid 3.11.6.1.5 reaction medium for intercalation reactions 3.1 1.6.1 solutions of alkali metals 3.11.6.2 Ammonium cations intercalation of 3.11.6.1.5 Ammonium polysulfide preparation 3.7.3.6 reagent for polysulfide synthesis 3.7.3.6 Antiarthritic agents 3.7.3.6 Aromatic amines intercalation of 3.11.6.1.6 Auranofin synthesis of 3.7.3.6 Aurivillius phases 3.10.3.2
B Batteries applications 3.11.6.1 Binary acids in formation of chalcogenides 3.7.4.3 Binary compounds of group IA and IIB metals 3.7.4.2.1 Binary oxides crystallographic shear structures 3.10.3.1 of transition metals 3.10.2.2 rutile related 3.10.3.1.1 with wide compostion range 3.10.2.2 Binary sulfides formation 3.7.3.6 Bivariant thermodynamical behavior 3.10.1.5.4 Block structures in metal oxides 3.10.1.3.1, 3.10.3.1.3, 3.10.1.5.4 splat cooled 3.10.3.1.3 stoichiometry of 3.10.3.1.3 Bond strength xenon oxygen 3.9.1 Borates as ligand transfer agents 3.9.3 Borohydrides reducing anions for intercalation reactions 3.1 1.6.1.5
Boron trifluoride oxidation 3.8.3.4.2 Bromopentafluorobenzene reaction with nickel atoms 3.8.2.11.2 reaction with palladium atoms 3.8.2.11.2 Bronzes molybdenum oxides 3.10.3.2.4 red and blue 3.10.3.2.4 vanadium 3.10.4.2.4 Brownmillerite phases 3.10.3.2 Butyllithium as reagent for intercalation 3.1 1.6.1.4 as reducing agent 3.11.6.3 for lithium intercalation 3.11.6.1.1
C
Cadmium slurries in tetrahydrofuran 3.7.2.8 Carbon dioxide complexes with transition metals 3.8.2.11.3 insertion into metal ligand bonds 3.8.2.8.2 reactions with transition metal complexes 3.8.2.8.3 Carbon disulfide reactions with nickel 3.8.3.7.2 Carbon monoxide complexes with group IB and IIB metals 3.7.2.8 Cathodes of batteries 3.1 1.6 Cation relaxation shear plane stability 3.10.1.2.3 Chain host lattices 3.11.6 Chalcogenides alloy phases 3.11.1 bonding in 3.11.1, 3.11.2 chemical vapor transport of 3.11.3.2 ferromagnetic 3.11.2.2 formation of 3.11.6, 3.8.4 from reactions of melts 3.11.7 metallic and semimetallic 3.11.1 metal, synthesis and crystal growth 3.11.2.3, 3.11.3.1 metastable compounds, Table 3.11.7.2 syntheses involving metals 3.11.4.1 synthesis under supercritical conditions 3.11.5 transition metal and rare earth 3.11.1 Charge carriers and electrical conductivity 3.10.1.5.1 Charge compensation 3.10.2.3.1,3.10.2.3.3 Charge density wave induced by an intercalate 3.1 1.6.1.2 Chemical analysis for Zn, Cd and Hg 3.7.3.5.1
Subject Index Chemical twinning 3.10.1.3.3 Chemical vapor transport of chalcogenides 3.11.1, 3.11.3.2 thermodynamic rules for 3.1 1.3.2 transporting agents 3.11.3.2 Chevral phase synthesis of 3.1.3. Clustering 3.10.2.3.5 Clusters cubane types 3.8.3.6.1 from defect interactions 3.10.1.5.2 metal sulfides 3.8.3.6.1 ofgroup IB and IIB metals 3.7.3.1.1, 3.7.3.1.2, 3.7.3.2. 3.7.3.3. 3.7.3.4.1 of transtion and inner transition metals 3.8.3.2.1 Coherently intergrown structures 3.10.1.5.4 and non-stoichiometry 3.10.1.5.4 and ordered extended defects 3.10.1.4.1 lammelar 3.10.1.4.1 with inhomogeneous crystallites 3.10.1.5.4 wrong blocks 3.10.1.4.2 Coinage metals reaction with water 3.7.2.2.1 Cointercalated compounds 3.1 1.6.1.5 Colloid formation 3.1 1.6.3 metal sulfides 3.8.3.6.1 Complex(es) of Cu(II1) 3.7.3.1.2 oxides 3.10.3.3.5 Composite compounds 3.1 1.6.1.4 Compounds interstitial 3.11.6 Conduction bands in ionic oxides 3.10.1.1.1 in metallic chalcogenides 3.1 1.2.2 in metallic conductors 3.10.3.5 Copper intercalation compounds of 3.11.6.1.2 macrocyclic complexes 3.7.2.1.2 mixed valence complexes 3.7.3.1.1,3.7.3.1.2 slurries in tetrahydrofuran 3.7.2.8 Covellite synthesis of 3.7.3.6 Crown ethers complexes of 3.7.2.5, 3.8.2.7.1 reactions with metal halides 3.7.2.5 Cryptands complexes of transtion and inner transition metals 3.8.2.7.1 reactions with metal halides 3.7.2.5 Crystal growth by arc imaging 3.10.2.2.1 by Bridgman technique 3.10.2.2.1
491
by fusion 3.10.2.2.1 techniques 3.10.2.2.1 Crystallographic shear (CS) disordered 3.10.1.4.2 homologous series 3.10.3.1.1 Mo and W oxides 3.10.3.1.2 planes 3.10.1.3.1,3.10.1.5.3, 3.10.3.1.2 plane displacement vector 3.10.1.3.1 plane indicies 3.10.1.3.1 rutile 3.10.3.1.1 structures 3.10.3.1.1 swing 3.10.3.1.1 wavelike 3.10.3.1.1 Crystals field splitting in metal chalcogenides 3.11.1. 3.11.2.2 relation to band structure 3.11.2.2 Cryptate complexes intercalation of 3.11.6.1.7 Cuprates containing lanthanides 3.10.3.2.1 high T, superconductors 3.10.3.2 Cyanine dyes intercalation of 3.11.6.1.7
D Defect(s) and crystallographic shear 3.10.1.3.1 and oxidation states 3.10.1.1.1 antistructure 3.10.1.1.1 clusters 3.10.1.5.2 dependence on fugacities 3.10.1.1.2 equlibria in solids 3.10.1.1.1 extended 3.10.1.3.1,3.10.1.4.2 F-centers 3.10.1.1.1 foreign atoms 3.10.1.1.1 formation of clusters 3.10.1.5.2 holes 3.10.1.1.1 in solids 3.10.2.3.1 interactions 3.10.1S.2 interactions in solids 3.10.1.2 intergrowth 3.10.1.4.1 interstitial 3.10.1.1.1 of lanthanum oxides 3.10.3.2.3 planar 3.10.1.3.1,3.10.1.5.4 polarization-polarons 3.10.1.1.1 structures and density measurements 3.1 1.2.2 structures and theory of 3.10.1.2.3 Deintercalation 3.11.6. 3.11.6.1.5,3.11.6.2, 3.11.6.4.1,3.11.6.4.2 Dialkyl selenides, reaction with Hg 3.7.4.6.1 tellurides. reaction with group IB and IIB compounds 3.7.4.6.2.2
492
Subject Index
Dialkyl metal complexes reactions with alcohols or acids 3.7.2.3.1 Dichalcogenides 3.11.6, 3.1 1.6.1. 3.11.6.1.1, 3.11.6.1.2, 3.11.6.1.5 layered 3.11.6.1.7 layered transtion metal 3.1 1.6.1 transition metal 3.11.6.1 Diffraction continuous variation with T or composition 3.10.3.4.1 incommensurate 3.10.3.4 superstructure 3.10.3.4 Diffusivity and ionic conductivity 3.10.1.1.3 Diketones complexes with transition and inner transition metals 3.8.2.7.1 in metal oxidation reactions 3.8.2.7.2 Dilatometer 3.1 1.6.1.7 Dimethylcarbonate as solvent for intercalation 3.11.6.1.1 Dioles cointercalated alkali metal compounds 3.11.6.1.5 Dioxygen bonding to hemocyanine 3.7.2.1.2 to hemoglobin 3.8.2.1.2 complexes of porphyrins 3.8.2.1.2 of Schiff-bases 3.8.2.1.2 with Group IB and IIB metals 3.7.2.8. 3.7.2.1.2 with transition metals 3.8.2.11.3, 3.8.2.1.2 in oxidative-addition reactions 3.8.2.1.2 reactions in the solid state 3.8.2.1.2 Diphenyl selenides and tellurides use in MOCVD 3.7.4.7 Dithiocarbamates ligand replacement reactions 3.8.3.4.2 Ni(1V) complexes 3.8.3.4.1 of group IB and IIB metals, Table 3.7.3.4 oxidation of low valent metal complexes 3.8.3.4.1 reaction with halogens 3.7.3.4.1 reactions with CS2 3.8.3.4.3 with transition and inner transition metals 3.8.3.4 Dithiocarboxylates by sulfur abstraction 3.7.3.4.2 oxidation 3.7.3.4.1 with Group IB and IIB elements 3.7.3.4 with transition and inner transition metals 3.8.3.4
1.1-Dithioethylenes mixed valence complexes 3.7.3.1.2 reactions with sulfur 3.7.3.1.2 with group I3 and IIB elements, Table 3.7.3.4 with transition and inner transition metals 3.8.3.4 Dithioketones with group IB and IIB elements 3.7.3.5 with transition and inner transition metals 3.8.3.5.1 1,2-Dithiolenes acyloin reactions 3.7.3.5.1 by ligand substitution 3.7.3.5.2 complexes of gold 3.7.3.6 from metal sulfides and alkynes 3.7.3.5.1 from the 1,l-dithioanion 3.7.3.5.1 of group IB and IIB elements 3.7.3.5 with transition and inner transition metals 3.8.3.5 Dithiolium salts synthesis of 3.7.3.5.1 Doping of solids 3.10.2.3.1 Double decomposition in formation of group IB and IIB tellurides 3.7.4.3.1 Double oxides based on tantulum pentoxide 3.10.3.4.2 Double Re03 type systems structural types 3.10.3.2.4.4
E
Electrical conductivity and charge carriers 3.10.1.5.1 pressure dependence 3.10.1.5.1 Electrochemical from aqueous solutions 3.11.6.1.2 intercalation 3.11.6, 3.11.6.1.1. 3.11.6.1.5. 3.11.6.1.7 oxidation reactions 3.8.3.4.1 reduction, intercalation 3.10.4.2.4 Electrointercalation 3.1 1.6, 3.1 1.6.4.1 using acetonitrile as solvent 3.11.6.1.1 Electrolytes nonaqueous 3.11.6.4.2 Elecrolytic reactions in formation of tellurides 3.7.4.1.3 Electron diffraction of tantalum and niobium oxides 3.10.3.4.2 Electrooxidation of metal compounds 3.7.4.6.1.2 Energy gaps in ionic oxides 3.10.1.1.1
Subject Index Equilibrium diagrams of niobium-zirconium oxides 3.10.3.4.1 of tantalum oxides 3.10.3.4.2 Ethers cointercalated alkali metal compounds 3.11.6.1.5 Ethylenecarbonate as solvent for electrointercalation 3.11.6.1.1 EXAFS 3.11.6.3 Exfoliation 3.11.6,3.11.6.1.4,3.11.6.1.5 Extended defect structures 3.10.1.2.3 in equilibrated structures 3.10.1.2.3 kinetics of formation 3.10.1.2.3 microstructure 3.10.1.4.2 nucleation 3.10.1.2.3 ordered 3.10.1.4.2 oxygen vacancy concentrations 3.10.1.2.3 random intergrowth 3.10.1.4.2 theory of 3.10.1.2.3 thermodyanimcs of 3.10.1.2.3
F Ferrites 3.10.2.3.2, 3.10.3.2.2 hexagonal 3.10.3.2 industrial applications 3.10.3.2.2 sequences in, Table 3.10.3.2.2 structures of 3.10.3.2.2 Flocculation 3.1 1.6,3.11.6.1.S,3.11.6.1.6. 3.11.6.1.7 Fluorites 3.10.2.3.4 commensurate super structures 3.10.2.2.2 modeled as ccp array 3.10.2.2.2 oxygen deficient related structural types 3.10.3.2.2 oxygen excess realted structural types 3.10.3.2.3 related structures 3.10.2.2.1 Frameworks three-dimensional 3.11.6 Fugacities and defect concentrations 3.10.1.1.2 effects on oxide equilibria 3.10.1.1.2 Fused salts 3.11.6.1.1
G
Gallium polyoxycations 3.11.6.1.7 Gold liquid 3.7.3.2 thiolates 3.7.3.2, 3.7.3.3 Gold thiolates in medicine 3.7.3.2,3.7.3.3 Grossly non-stoichiometric oxides factors in preparation of 3.10.1.5.2
493
Group IB and IIB Metals clusters 3.7.3.1.1, 3.7.3.1.2,3.7.3.2,3.7.3.3, 3.7.3.4.1 dithiocarbamate complexes, Table 3.7.3.4, dithiocarboxylate complexes, Table 3.7.3.4 1,l-dithioethylene complexes 3.7.3.4 1.2-dithiolene complexes 3.7.3.5 phosphorodithioate complexes 3.7.3.4 polysulfide complexes 3.7.3.2,3.7.3.3 thiocarbonyl complexes 3.7.3.3 thio complexes 3.7.3.2 thioether complexes 3.7.3.3
H
Hemocyanin reversible bonding to O2 3.7.2.1.2 Hemoglobin binding to 0,3.8.2.1.2 Hexamethylphosphoric acid triamide as solvent for alkali metal intercalation 3.11.6.1.1 High resolution electron microscopy 3.10.2.2.2 of metal oxides 3.10.3.4.2 High temperature superconducting cuprates 3.10.3.2.1 Hollandite as storage structures 3.10.1.3.2 tunnel structures 3.10.3.3.3 Homogeneity ranges 3.11.6 affect of temperature 3.10.1.5.2 of grossly non-stoichiometric oxides 3.10.1.5.2 Homologous series 3.10.1.5.3, 3.10.3.1.1, 3.10.3.1.2 Host lattices 3.11.6 neutral chalcogenides 3.11.6 Host structures layered 3.11.6 Hydrated ions intercalation of 3.11.6.1.5 Hydrated sodium compounds intercalation of 3.11.6.2 Hydration 3.11.6.2,3.11.6.4.1 Hydrazine intercalation of 3.11.6.1.6 Hydrogen intercalation into metal oxides 3.10.4.2.4 Hydrogen bronzes synthesis of 3.11.4.2 Hydrogen peroxide catalyzed decomposition 3.7.2.3.1 reactions with metals 3.8.2.3.1 Hydrogen sulfide molecular coordination 3.8.3.2.1
494
Subject Index
Hydrogen sulfide (Continued) in synthesis of sulfide complexes 3.8.3.2.1. 3.8.3.6.1 Hydrolysis 3.11.6.1.5 of metal ligand bonds 3.7.2.2.2. 3.8.2.2 xenon fluorides and oxyfluorides 3.9.2 Hydrothermal synthesis of chalcogenides, in aqueous solution 3.11.5.1 Hydroxides formation in ligand substitution reactions 3.7.2.7.1
I Incommensurate structures 3.10.1.5.5 metal oxides 3.10.3.4 of chalcogenides 3.11.4.2 Indium alloys, intercalation from 3.11.6.1.2 Infinitely adaptive structures 3.10.1.5.3. 3.10.1.5.5 oxide phases 3.10.3.4 vernier types 3.10.3.4 Inner transition metals alcoholysis of metal-ligand bonds 3.8.2.4.1 alkoxide complexes 3.8.2.10.1 dithiocarbamate complexes. Table 3.7.3.4 dithiocarboxylate complexes, Table 3.7.3.4 1,l-dithioethylene complexes 3.7.3.4 1.2-dithiolene complexes 3.7.3.5 hydrolysis of metal-ligand bonds 3.8.2.2.2 insertion into metal-ligand bonds 3.8.2.6.2 oxidation of metal-ligand bonds 3.8.2.4.3 substitution of metal ligand bonds 3.8.2.2.1, 3.8.2.4.1.3.8.2.6.1 Insertion reactions 3.11.6 by CS2 into metal amides 3.8.3.4.3 involving metal-ligand bonds 3.8.2.6.2 0 2 insertion into transiton metal-ligand bonds 3.8.2.1.3 0 2 insertion into group IB and IIB metal ligand bonds 3.7.2.1.3 Intercalate ion ordering 3.11.6.1.2 Intercalation by redox methods 3.11.6.2 compounds 3.11.6, 3.11.6.1.7 containing Hz 3.10.4.2.4 layered stacking 3.11.6.1.1 of copper 3.11.6.1.2 of group IIIA and VA metals 3.11.6.1.2 of mercury 3.11.6.1.2 of post transition metals 3.11.6.1.2 of silver 3.11.6.1.2 of transition metals 3.10.4.2.4.3.1 1.6.1.2. 3.1 1.6.1.4. 3.11.6.2
structural deformations 3.1 1.6.1.1. 3.11.6.1.2 using ammonia as solvent 3.11.6.1 electrochemical, with light 3.11.6, 3.11.6.1.1 in titanates 3.10.3.2.4 kinetics of reactions 3.1 1.6 of alkali metals 3.11.6.1 of alkylamines 3.1 1.6.1.4 of amines 3.11.6.1.6 of ammonia 3.11.6.1 of ammonium compounds 3.11.6.1.5 of cryptate complexes 3.11.6.1.7 of hydrocarbons 3.1 1.6.1.7 of hydrogen 3.10.3.2.4 of isocyanides 3.11.6.1.6 of metallocenes 3.11.6.1.7. 3.11.6.2 of organic molecules 3.11.6.2 of rare earth metals 3.11.6.1.4 mechanism and kinetics of 3.1 1.6 Incommensurate phases 3.10.1.5.5 Infinitely adaptive structures 3.10.1.5.5. 3.10.3.4 and pseudo-bivariant behavior 3.10.1.5.5 rotating shear planes 3.10.1.5.5 Insertion reactions aldehydes into metal-ligand bonds 3.7.2.4.2 3.7.2.4.2 of main group element oxides into metal ligand bonds 3.7.2.6.3 ketones into metal-ligand bonds 3.7.2.4.2 Interface energy relationship to free energy 3.10.1.5.4 Intergrowth coherent 3.10.1.4.1. 3.10.1.5.4 disordered 3.10.1.4.2 homologous series formed by 3.10.1.4.1 in perovskite strucutres 3.10.1.4.1 of perovskites with rock salt layers 3.10.3.2.1 ordered 3.10.1.4.1 Interstitial atoms 3.11.6 compounds 3.11.6 metals and anti-phase boundries 3.10.1.2.3 mobility of atoms 3.1 1.6 Ion exchange 3.10.2.3.5,3.1 1.6, 3.1 1.6.1.7, 3.11.6.2.3.11.6.4.2 in titanates 3.10.3.2.4 Ionic conductivity related to diffusivity 3.10.1.1.3 Ionizing radiation synthesis of non-stoichiometric oxides 3.10.2.1 Isocyanides intercalation of 3.1 1.6.1.6
Subject Index
J
Jahn-Teller effects 3.10.2.3.2
K Kinetic(s) effects on surface layers 3.11.2 of intercalation reactions 3.11.6 Krypton fluorides 3.9.4 oxygen bonds in compounds 3.9.4
L
Lanthanide(s) cuprates of 3.10.3.2.1 oxidation with 0,3.8.2.1.1 oxides properties and synthesis, Table 3.10.2.2.2 unit cell content, Table 3.10.3.2.2 Lattices chain host 3.11.6 changes in cohesive energy, Table 3.10.1.2.3 Layered dichalcogenides of transition metals 3.11.6.1.1 host structures 3.11.6 oxides 3.10.3.2 misfit compounds 3.11.6.1.4 sheets, in oxides 3.10.3.2 stacking 3.1 1.6.1.1 structures, edge-sharing octahedra 3.10.4.2.4 structures, polyhedral sheets 3.10.3.2 Ligand displacement reactions with amine and phosphine oxides 3.7.2.4.1 with ethers 3.7.2.4.1 with ketones 3.7.2.4.1 Low dimensional behavior, in molybenum bronzes 3.10.4.2.4 Low-valent metal complexes oxidation of 3.8.3.4.1 Ludwigite 3.10.1.3.3
M
Macrocycles complexes of copper 3.7.2.1.2 complexes of transition and inner transition metals 3.8.2.7.1 Main group element oxides reactions with transition metal complexes 3.8.2.8.1 Mercaptides as ligands in chalcogenide complexes 3.7.3.6 coordination to metals 3.7.3.6 polymeric forms, in synthesis 3.7.3.6
495
Mercury captans 3.7.3.2 Metal atoms reaction with CO 3.7.2.8 reaction with 0,3.7.2.8 reaction with cyclohexene oxide 3.8.2.11 reaction with hexafluoroacetic anhydride 3.8.2.11.2 reaction with aryl halides 3.8.3.7.2 reaction with SiS 3.7.3.7 reactions with small-molecule organic substrates 3.8.3.7 Metal carbonyl complexes reactions with N 2 0 4 3.8.2.8.3 Metal chalcognides from metal compounds and chalcogenides 3.11.4.2 from metals and chalcogenides 3.11.4.1 Metal deficient sulfides synthesis of 3.8.3.1.2,3.8.3.2.1 Metal halide reactions with main group element oxides 3.8.2.8.1 Metal hydroxides precipitation of 3.8.2.9.1 solubility products, Table 3.8.2.9.1 Metal-ligand bonds carbon dioxide reactions with 3.8.2.8.2 insertion into 3.7.2.4.2 reactions with main group element oxides 3.7.2.6.3 Metallocenes insertion reactions with 0, 3.8.2.1.3 intercalation of 3.11.6.1.7 Metal oxide(s) and defects 3.10.1.5.1 formation of Group IB and IIB compounds 3.7.2.1.1 formation of lanthanide compounds 3.8.2.1.1 formation of transition metal compounds 3.8.2.1.1 homogeneity ranges 3.10.1.5.1 homologous series 3.10.1.5.3 with modulated structures 3.10.1.5.5 Metal selenides bonding in 3.11.1, 3.11.2 synthesis of 3.7.4. 3.8.4, 3.11.3 Metal sulfides bonding in 3.11.1. 3.11.2 synthesis of3.7.3. 3.8.3. 3.11.3 Metal tellurides bonding in 3.11.1, 3.11.2 synthesis of 3.7.4. 3.8.4, 3.11.3 Metal thiolates formation of 3.7.3.6
496
Subject Index
Metastability 3.10.2.3.2,3.10.2.3.5 Metastable chalcogenides, Table 3.1 1.7.2 Metastable products 3.11.6 Misfit layer compounds 3.1 1.6.1.4 Mixed thiolate ligand complexes 3.7.3.5.2 Mixed valence complexes of copper 3.7.3.1.1.3.7.3.1.2 of 1.1-dithioethylenes 3.7.3.1.2 Mixed valence compounds 3.1 1.6.3 MOCVD 3.7.4.6.2.2,3.7.4.7 Modulated structures 3.10.1.5.5 Molten metals in synthesis of metal sulfides 3.11.7.2 Molybdenum bronzes 3.10.4.2.4 oxides 3.10.4.2.4 blue and red bronzes 3.10.3.2.4 tunnel strucutres 3.10.3.3 Multiple oxides and doping 3.10.2.2.2 defect complex equilibria 3.10.2.2.2 point defects 3.10.2.2.2
N
Nanoparticles synthesis of chalcogenides 3.1 1.5.1 Neutron diffraction of tantalum oxides 3.10.3.4.2 Nickel slurries use of in synthesis 3.8.3.7.2 Niobium oxide related structures 3.10.3.1.3 Nitrogen oxides reactions with metals 3.8.2.8.3 Non-aqueous solvents 3.11.6, 3.11.6.1.1 electrochemical intercalation from 3.1 1.6.1.2 Non-stoichiometry 3.10.1.2.1,3.10.2.3.2, 3.10.2.3.3,3.10.2.3.4,3.10.2.3.5.3.11.6 adaptive structures 3.10.3.4 and mass transport 3.10.1.1.3 and physical properties 3.10.1.1.3 classical 3.10.1.5.4 classification 3.10.1.5 classification of oxides 3.10.1.5 composition ranges 3.10.1.5.1, 3.10.1.5.2 compounds and bivariant behavior 3.10.1.5 control of in metal chalcogenide synthesis 3.11.2.3 dependence on T and fugacity 3.10.2.2.1 disordered compounds 3.10.1.3.2 grossly non-stoichiometric 3.10.1.5.2 in chalcogenides 3.11.4.1 layered oxides 3.10.3.2
of tantalum oxides 3.10.3.4.2 operational definition 3.10.3 ordered compounds 3.10.1.3.2 oxide phases 3.10, 3.10.1.5.4. 3.10.2.2.1. 3.10.3.5 phase diagrams 3.1 1.2.3 structural definition 3.10.1.5 sulfides and selenides 3.11.1 thermodynamic definition 3.10.1.5 thermodynamic details 3.10.2.2.1 T i 0 phase as model 3.10.2.2.1 tunnel structures 3.10.1.3.2 uranium oxides 3.10.3.4.3 using ionizing radiation 3.10.2.1 with altervalent anions 3.10.3.5 with twinned structures 3.10.1.3.3 Nuclear medicine 3.8.3.4.2 Nuclear quadrupole interaction 3.11.6.1.2
0
Oil additives phosphorodithioates 3.7.3.4.2 Ordered phases characteristics of 3.10.1.5.3 infinitely adapted structures 3.10.1.5.3 Organometallic complexes sulfides 3.8.3.2.1, 3.8.3.4.2 Organoselenols reactions with group IIB compounds 3.1.4.6.2.3 Organosols 3.8.3.6.1 Oxidation reactions electrochemical 3.8.3.4.1 of group IB and IIB metals with hydrogen peroxide 3.7.2.3 of group IB and IIB metals with O2 and 0 3 3.7.2.1.1 of lanthanides with O2 and O3 3.8.2.1.1 of metal-ligand bonds 3.8.2.4.3 of metals and complexes 3.7.2.7.2 of transition metals with O2 and O3 3.8.2.1.1 Oxidative addition of Hg by chalcogenides 3.7.4.6.1 Oxides double 3.10.3.4.2 lanthanum 3.10.2.2.2 main group element dissolution of group IB and IIB metals 3.7.2.6.1 reactions with metals 3.7.2.6.1 metal rich 3.10.2.1 nitrogen oxide reactions with metal halides 3.7.2.6.2 non-stoichiometric 3.10
Subject Index of uranium 3.10.3.4.3 oxygen deficient 3.10.2.1 phases with narrow compositional ranges 3.10.1.5.1 treatment with H2S 3.11.6.1.1 transition metal homogeneity ranges. Table 3.10.2.2.1 with adaptvie structures 3.10.3.4.1 Oxyborates 3.10.1.3.3 Oxygen abstraction reactions 3.8.2.6.3 deficient lanthanum oxides 3.10.2.2.2 insertion into group IB and IIB metal-ligand bonds 3.7.2.1.3 insertion into transition metal-ligand bonds 3.8.2.1.3 reaction with group IB and IIB metals 3.7.2.1.1 reaction with lanthanides 3.8.2.1.1 reaction with transition metals 3.8.2.1.1 sources, for Xe-0 bonds 3.9.2 Oxygen donor ligands in ligand substitution reactions 3.8.2.6.1 Ozone reactions with colloidal Ag 3.7.2.1.1 with transition metals 3.8.2.1.2
P Pentagonal columns 3.10.1.3.2,3.10.1.4.2 Periodicity incommensurate 3.11.6.1.4 Peritectoidal decomposition intermediate oxides, at high T 3.10.2.2.2 Perovskite(s) 3.10.2.3.1,3.10.2.3.3 disordered 3.10.1.4.2 layered structures 3.10.3.2 oxides, ordered 3.10.1.4.2 twinned structures 3.10.1.3.3 Peroxides reactions with metal metallocenes 3.8.2.5.1 reactions with transition metals 3.8.2.9.2 Perxenates decomposition 3.9.2 reactions 3.9.2 synthesis 3.9.2 Phase(s) Aurivillius 3.10.3.2 brownmillerite 3.10.3.2 Chevrel 3.7.3.6 diagrams 3.11.3.1 higher stage 3.11.6.1.1 of selenides and tellurides 3.7.4.1. 3.7.4.1.2 ordered in Pr oxides 3.10.1.5.3 Ruddlesden-Popper 3.10.3.2
497
rule for non-stoichiometric oxides 3.10.1.5 Phosphate bronzes crystal twinning 3.10.1.3.3 Phosphines gold(1) sulfide complexes 3.7.3.2 reactions with sulfur-rich complexes 3.7.3.4.2, 3.8.3.4.2 Phosphorodithioates as oil additives 3.7.3.4.2 ligand replacement reactions 3.8.3.4.2 of group IB and IIB elements, Table 3.7.3.4.1 of transition and inner transition metals 3.8.3.4 P hthalocyanines oxidation of group IB and IIB metal complexes 3.7.2.3.2 Physiological relevance 3.7.3.2, 3.7.3.3 of nuclear medicine, T, derivatives 3.8.3.4.2 Pinakiolite 3.10.1.3.3 Planes crystallographic shear 3.10.1.2.1 Point defects 3.10.1.5 aggregation 3.10.1.2.1 and electron bond equiliria 3.10.1.1.1 as charge compensators 3.10.1.2,3.10.1.2.1 notation for 3.10.1.1.1 Polarons in crystals 3.10.1.1.1 Polychalcogenides formation of 3.8.4 Polyethers reactions with metals 3.7.2.5 Polymeric oximes as ligands to transition metals 3.8.2.1.2 Polymorphs of tantalum oxides 3.10.3.4.2 Polypropylene as solvent for colloid formation 3.11.6.3 Polysulfide(s) anions, for synthesis of metal sulfides 3.8.3.6.2 complexes, via oxidative decarbonylation 3.8.3.6.2 complexes from sulfates and H2S 3.8.3.2.1 complexes from thiometallates 3.8.3.6.2 formation of 3.7.3.6 metal complexes, from polysulfide anions 3.7.3.6 of group IB and IIB elements 3.7.3.2. 3.7.3.3 of transition and inner transition metals 3.8.3.2 silver complexes 3.7.3.6
498
Subject Index
Polysulfide(s) (Continued) solutions 3.8.3.6.2 tetra and penta. of group IB and IIB elements 3.7.3.2. 3.7.3.3 Polytype formation 3.11.6.1.1 Post transition metals intercalation of 3.11.6.1.2 Precursor compounds 3.10.2.3.3 Psilmelane 3.10.3.3.3 tunnel structures 3.10.3.3.3 Pyrochlores 3.10.2.3.4
R Radon fluorides 3.9.4 oxygen bonds 3.9.4 Ramsdellite 3.10.3.3.3 relation to rutile structure 3.10.3.3.3 tunnel structures 3.10.3.3.3 Reactions insertion 3.1 1.6 topological 3.11.6 Redox intercalation 3.11.6.2 Ruddlesden-Popper phases physical properties 3.10.3.2.1 Rutile related structures 3.10.3.1.1
S
Salts fused 3.11.6.1.1 Segregation 3.10.2.3.5 Selenides non-stoichiometric 3.11.1 Selenium compounds reactions with group IB and IIB compounds 3.7.4.4. 3.7.4.5. 3.7.4.6 Semiconductor(s) 3.10.2.3.1 chalcogenides 3.1 1.1 Zn and Cd compounds 3.7.4.1 Shear planes cation relaxation 3.10.1.2.3 crystallographic 3.10.1.2.1 detection by electron microscopy 3.10.1.2.2 formation 3.10.1.2.1 in rutile type oxides 3.10.1.2.2 relationship to point defects 3.10.1.2.1 relaxation of 3.10.1.2.2 stabilities 3.10.1.2.3 swinging 3.10.1.2.2 Silver intercalation compounds of 3.11.6.1.2
Silver slurries in tetrahydrofuran 3.7.2.8 Site occupancy interstitial 3.10.1.1.1 vacancies 3.10.1.1.1 Sodium dithionite as reducing agent for intercalation 3.11.6.2 Soft chemistry 3.11.6 Solids defect chemistry 3.10.1.1.1 defect equilibria 3.10.1.1.1 doping of 3.10.2.3.1 Solid solutions adaptive compounds 3.10.1.5.5 of oxides 3.10.1.5.5 Solubility of group IB and IIB metal hydroxides, Table 3.7.2.7.1 Solvation reactions 3.11.6, 3.1 1.6.2 Solvents exchange reactions 3.11.6.2 non-aqueous 3.11.6 Sphalerite structural analogs 3.7.3.6 Spinels defect structures 3.10.2.3.2 inverse 3.10.2.3.2 normal 3.10.2.3.2 structure of 3.10.2.3.2.3.10.3.2 Stoichiometric oxides energy gaps 3.10.1.1.1 Stoichiometry small deviations from 3.10.2.1 Structural transformations 3.11.6.4.2 in intercalation compounds 3.11.6.1.1 Structural transitions 3.1 1.6.3 Structure(s) incommensurate 3.10.1.5.5 infinitely adaptive 3.10.1.5.3. 3.10.1.5.5, 3.10.3.4 pinned vernier 3.10.3.4.1 modulated 3.10.1.5.5,3.10.3.4.1 Re03 related 3.10.3.1.2 rutile related 3.10.3.1.1 shear types 3.10.3.4.2 site vacancies 3.10.1.1.1 superstoichiometric 3.10.3.4.1 tunnel 3.10.1.3.2.3.10.3.3 twinned 3.10.1.3.3 vernier 3.10.1.5.5,3.10.3.4.1 Sublattices of oxides 3.10.1.2.1 Sulfide(s) anionic ligands 3.7.3.6
Subject Index anionic, tetra 3.8.3.6.1 biologically relevant 3.8.3.2.1 bridging ligands 3.8.3.6.1 clusters 3.8.3.6.1 formation from sulfur 3.7.3.1.1,3.8.3.1.1, 3.8.3.1.2 formation with aqueous metal ions and H2S 3.7.3.2 from H 2 S 3.8.3.2.1 metal. as ligands 3.8.3.6.1 metal. from thiolates 3.8.3.6.3 metal deficient 3.8.3.1.2,3.8.3.2.1 minerals 3.7.3.1.1 non-stoichiometric 3.11.1 of group IB and IIB elements 3.7.3 of transition and inner transition metals 3.8.3, 3.8.3.6 organometallic complexes 3.8.3.2.1. 3.8.3.4.2 salts. in synthesis 3.8.3.6 es in water, Table 3.7.3.2, ternary species, of Cu and Ag 3.7.3.1.1 thioanions 3.8.3.6.1 Sulfur reactions with 1.1-dithioethylene 3.7.3.1.2 Sulfur dioxide reactions with metal-ligand bonds 3.8.2.8.2 reactions with metals 3.8.2.8.3 Sulfur rich complexes of group IB and IIB elements 3.7.3.1, 3.7.3.3 from ammonium polusulfides 3.7.3.4.2 from reaction of S with metal complexes 3.7.3.1.2 from reaction with oxidants 3.7.3.1.2 reaction with phosphines 3.7.3.4.2 of transition and inner transition metals 3.8.3.4 from insertion into metal-ligand bonds 3.8.3.2.2 from ligand replacement reactions 3.8.3.4.2 from substitution reactions 3.8.3.2.1 with phosphines 3.7.3.4.2, 3.8.3.4.2 Superconductors 3.11.6.1.2,3.11.6.1.6. 3.11.6.1.7 cuprates, high T , 3.10.3.2.1 molybdenum bronzes 3.10.4.2.4 SLpercritical conditions s) nthesis under 3.11.5 Suprrlattices du.: to ion ordering 3.11.6.1.2 Superoxo-bridged complexes 3.8.2.1.2 Superstructures in 1%ntalum and tungsten oxide. 3.10.3.4.2
499
of uranium oxides 3.10.3.4.2 Swelling 3.11.6.1.5 Symmetrization reactions 3.8.3.4.2
T
Tantulum pentoxide related phases 3.10.3.4.2 Tellurides non-stoichiometric 3.1 1.1 Ternary compounds formation, with Cu and Au 3.7.4.1.4 Ternary sulfides of Cu and Ag 3.7.3.1.1 Tetrahydrofuran as solvent for electrointercalation 3.11.6.1.1 Thiocarbonyl group IB and IIB element complexes 3.7.3.3 Thioether group IB and IIB element complexes Thiolates chelating, in synthesis 3.8.3.6.3 homoleptic, metal complexes 3.8.3.6.3 in metal sulfide synthesis 3.8.3.6.3 mixed ligand complexes 3.7.3.5.2 Thiols clusters 3.7.3.2 complexes of Group IB and I I B elements 3.7.3.2 in metal sulfide synthesis 3.8.3.6.1 Thiospinels 3.1 1.6.1.2 Thiourea complexes of group IB and IIB elements 3.7.3.3 sulfur-rich complexes 3.7.3.3 Thioxanthates complexes of group IB and IIB elements 3.7.3.4. Table 1 complexes of transition and inner transition metals 3.8.3.4.2 Thiuramdisulfide oxidation 3.7.3.4.1 Titanates 3.10.2.3.1 ion exchange properties 3.10.3.2.4.6 with layered structures 3.10.3.2.4.6 Titanium bronzes tunnel structures 3.10.3.3.2 Topological reactions 3.11.6 Transalcoholysis of metal complexes 3.8.2.4.1 Transition metal(s) alcoholysis of metal-ligand bonds 3.8.2.4.1 clusters 3.8.3.2.1 dichalcogenides 3.11.6.1. 3.1 1.6.1.1 dithiocarbamate complexes, Table 3.7.3.4 dithiocarboxylate complexes, Table 3.7.3.4
500
Subject Index
Transition metal(s) (Continued) 1.1-dithioethylene complexes 3.7.3.4 1.2-dithiolene complexes 3.7.3.5 hydrolysis of metal-ligand bonds 3.8.2.2.2 oxidation of metal-ligand bonds 3.8.2.4.3 oxidation with O2 and O3 3.8.2.1.1 oxides 3.10.2.2.1 phosphorodithioate complexes 3.7.3.4 polysulfide complexes 3.8.3.2 reactions with 0, 3.8.2.1.2 substitution of metal-ligand bonds 3.8.2.2.1,3.8.2.4.1 sulfides 3.8.3 from sulfide salts 3.8.3.6 Transition metal atoms reactions with organic substrates 3.8.2.11 Triphenylphosphine reaction with group IB and IIB compounds 3.7.4.6.2.6 Trithicarbonates complexes of group IB and IIB elements 3.7.3.4, Table 1 Tungsten bronzes hexagonal 3.10.1.3.2. 3.10.1.4.1 intergrowth 3.10.1.3.2. 3.10.1.4.1 square 3.10.1.3.2 tetragonal 3.10.1.3.2 tunnel structures 3.10.3.3 with pentagonal tunnels 3.10.1.3.2 Tunnel structures hexagonal, pentagonal and square 3.10.!.3.2 oxides with 3.10.3.2 structures of oxides 3.10.3.3 Twinning glide, plane type in crystals 3.10.1.3.3 NaCl type 3.10.1.3.3 repeated 3.10.1.3.3 rutile 3.10.1.3.3 Two-dimensional structures with anion chains 3.10.3.4.3
U
Unit cell content of lanthanide oxides, Table 3.10.2.2.2 subcell variation 3.10.3.4.1 Uranates non-stoichiometric 3.10.3.4.3
V
Vacancies anion andcation 3.10.1.1.1.3.10.1.5.3, 3.10.2.3.3,3.10.2.3.4. 3.10.2.3.5 equilibrium processes 3.10.1.1.1 in solids 3.10.2.3.1, 3.10.2.3.2 pairs 3.10.1.1.1 Vacancy disks 3.10.1.2.1 Valence bands in ionic oxides 3.10.1.1.1 Valence states and variation in nonstoichiometry 3.11.2.2 Vanadium bronzes 3.10.3.2.3, 3.10.3.3.4 oxides, synthesis and properties 3.10.4.2.4 Vapor phase transport 3.1 1.6.1.3. 3.11.6.1.4 Vernier structures 3.10.1.5.5 and adaptive structures 3.10.3.4 Vulcanization 3.7.3.4.2
w
Wurtzite structural analogs 3.7.3.6
x
Xanthates complexes of group IB and IIB elements. Table 3.7.3.4 copper(1) polymer 3.7.3.3 dixanthogen reactions 3.7.3.4.1 reactions with KSPh 3.7.3.2 complexes of transition and inner transition metals 3.8.3.4 by insertion of CS, or P4Slo3.8.3.4.2 ligand replacement reactions 3.8.3.4.2 Xenon oxides 3.9.2 oxyfluorides 3.9.2 pentafluorotellurates 3.9.3 pentfluoroselenates 3.9.3 Xenon-oxygen bonds oxygen sources 3.9.2
Z
Zinc slurries in tetrahydrofuran 3.7.2.8 Zirconia phases 3.10.3.4.1