Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 37

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 37

A Specialist Periodical Report

Spectroscopic Properties of Inorganic and Organometallic Compounds Volume 37 A Review of the Literature Published up to Late 2003 Senior Reporter G. Davidson, Department of Chemistry, University of Nottingham, UK Reporters K.B. Dillon, University of Durham, UK D.W.H. Rankin, University of Edinburgh, UK H.E. Robertson, University of Edinburgh, UK

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ISBN 0-85404-446-9 ISSN 0584-8555 A catalogue record for this book is available from the British Library

0The Royal Society of Chemistry 2005 All rights reserved

Apart from any fair dealing for the purpose of research or private study, or criticism or review as permitted under the terms of the U K Copyright, Designs and Patents Act, 1988, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the U K , or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the U K . Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page. Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 OWF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Typeset by Vision Typesetting Ltd, Manchester, UK Printed by Athenaeum Press Ltd, Gateshead, Tyne and Wear, UK

Preface

This thirty-seventh volume in the series of Specialist Periodical Reports on the ‘Spectroscopic Properties of Inorganic and Organometallic Compounds’ is a slimmer volume than its predecessors. This is because it has not proved possible to cover the NMR chapters this year. However, this is a temporary situation, and NMR will return to take its place in Volume 38. I am most grateful to my remaining fellow reporters, and to the staff of the Royal Society of Chemistry for all their assistance. George Davidson November 2004

V

Contents

Chapter 1 Nuclear Quadrupole Resonance Spectroscopy By K.B. Dillon 1 Introduction 2 Main Group Elements 2.1 Group 13 (Gallium-69 and Indium-115) 2.2 Group 14 (Germanium-73) 2.3 Group 15 (Nitrogen-14, Arsenic-75, Antimony-121 and -123, and Bismuth-209) 2.4 Group 17 (Chlorine-35 and -37, Bromine-79 and -81, and Iodine-127) 3 Transition Metals and Lanthanides 3.1 Manganese-55 3.2 Cobalt-59 3.3 Copper-63 and -65 3.4 Lanthanum-139 3.5 Praseodymium-151 References Chapter 2 CharacteristicVibrations of Compounds of Main Group Elements By G. Davidson

1

1 1 1 3

3 6 8 8 8 9 12 12 13

7 7 8 18 18 21 23 24 24 25 25 31

1 Group1 2 Group2 3 Group 13 3.1 Boron 3.2 Aluminium 3.3 Gallium 3.4 Indium 3.5 Thallium 4 Group14 4.1 Carbon 4.2 Silicon Spectroscopic Properties of Inorganic and Organometallic Compounds, Volume 37 0The Royal Society of Chemistry, 2005 vii

...

Contents

Vlll

4.3 Germanium 4.4 Tin 4.5 Lead 5 Group 15 5.1 Nitrogen 5.2 Phosphorus 5.3 Arsenic 5.4 Antimony and Bismuth 6 Group 16 6.1 Oxygen 6.2 Sulfur 6.3 Selenium 6.4 Tellurium 7 Group 17 8 Group 18 References Chapter 3 Vibrational Spectra of Transition Element Compounds By G. Davidson

1 Scandium, Yttrium and the Lanthanides 2 Titanium, Zirconium and Hafnium 3 Vanadium, Niobium and Tantalum 4 Chromium, Molybdenum and Tungsten 5 Manganese, Technetium and Rhenium 6 Iron, Ruthenium and Osmium 7 Cobalt, Rhodium and Iridium 8 Nickel, Palladium and Platinum 9 Copper, Silver and Gold 10 Zinc, Cadmium and Mercury 11 Actinides References Chapter 4 Vibrational Spectra of Some Co-ordinated Ligands By G. Davidson 1 2 3 4 5

Carbon, Silicon and Tin Donors Xenon Complexes Boron and Aluminium Donors Carbonyl Complexes Nitrogen Donors 5.1 Molecular Nitrogen, Azido- and Related Groups 5.2 Amines and Related Ligands 5.3 Ligands Containing >C = N-Groups 5.4 Cyanides, Isocyanides and Related Complexes 5.5 Nitrosyl Complexes

34 35 36 36 36 39 41 42 43 43 45 46 46 47 49 49 70

70 72 75 80 84 87 92 93 95 98 99 99

114

114 121 121 122 127 127 129 131 134 137

ix

Contents

6 Phosphorus and Arsenic Donors 7 Oxygen Donors 7.1 Molecular Oxygen, Peroxo, Aquo and Related Complexes 7.2 Carboxylate and Related Complexes 7.3 Keto-, Alkoxy-, Ether and Related Complexes 7.4 Ligands Containing 0-N, 0-P or 0-As Bonds 7.5 Ligands Containing 0-S or 0-Te Bonds 7.6 Ligands Containing 0-Cl or 0-1 Bonds 8 Sulfur and Selenium Donors 9 Potentially Ambident Ligands 9.1 Cyanates, Thio- and Selenocyanates and Their Iso-analogues 9.2 Ligands Containing N and 0,N and P or P and 0 Donor Atoms 9.3 Ligands Containing N and S Donor Atoms 9.4 Ligands Containing S and 0 Donor Atoms References Chapter 5 Gas-phase Molecular Structures Determined by Electron Diffraction By D. W.H. Rankin and H.E. Robertson

1 2 3 4 5 6 7

Introduction Compounds of Elements in Group 12 Compounds of Elements in Group 13 Compounds of Elements in Group 14 Compounds of Elements in Group 15 Compounds of Elements in Group 16 Compounds of Transition Elements, Lanthanides and Actinides References

139 140 140 141 144 145 146 147 147 149 149 149 153 154 155 173 173 174 175 176 179 183 186 189

1 Nuclear Quadrupole Resonance Spectroscopy BY K.B. DILLON

1

Introduction

This chapter reports on the pure nuclear quadrupole resonance (NQR) results for quadrupolar (I > i) nuclei in inorganic or organometallic solids. There has been a small decrease in the number of articles published compared with the previous year, with no major conference in this area taking place. One notable feature has been an increase in publications for some nuclei, such as "'In, and a decrease for the halogens C1, Br and I. The structure and strength of hydrogen bonds in inorganic solids have been reviewed, including results obtained by NQR spectroscopy.' Nuclear magnetic resonance techniques, including NQR, as a means for the non-destructive characterisation of materials, have been surveyed.2More specialised reviews have appeared on NQR (and NMR) studies of Cu nuclei in YbInCu4 under high press~re,~ and on recent NQR and high-field NMR results for 75Asnuclei in crystalline and glassy samples of arsenic chalcogenides? Patent applications have been filed for a transmit-receive coil system for NQR signal detection in substances and components thereof: for a receiving system for high q antennas in NQR and a method of detecting substances: for a scanner for NQR measurements and a method of detection for substances containing quadrupolar n ~ c l e ifor , ~ improvements to apparatus for NQR measurements,8 and for polarisation-amplified 14NNQR detection of TNT and other explosives in mines by using the quadrupole-quadrupole solid effect? The normal format is followed in the more detailed sections, with results for main group elements followed by those for transition metals and lanthanides.

2

Main Group Elements

2.1 Group 13 (Gallium-69 and Indium-115). - NQR spectra of 69Gaand 'I5In nuclei have been recorded for some GaSe and InSe layer compounds." The spectra were analysed, starting from polytypes of these compounds and the probability of formation of ordered structural fragments in the basic crystal modifications. As part of a study of Ni-Y intermetallics (Y = Al, Ga, In, Ti), 69Ga and "'In NQR frequencies (as appropriate) have been measured for Ni2Ga3, Spectroscopic Properties of Inorganic and Organometallic Compounds, Volume 37 0The Royal Society of Chemistry, 2005 1

2

Spectroscopic Properties of Inorganic and Organometallic Compounds

E-NiIn and Ni21n3.11The electric field gradient (efg) parameters were computed in advance, enabling rapid location of the experimental signals. The Ni2Y3structure requires two distinct Y sites, and these were observed for Y = G a and In. In the Ga compound, the linewidth for the Ga(2) site was more than three times that for the Ga(1) site. The lineshapes appeared distinctly Lorentzian for both compounds, possibly indicating the onset of intersite hopping at room temperature (RT). Line assignments were confirmed from the computed values. Two distinguishable In sites were also found for E-NiIn, and the results were in excellent agreement with computations using WIEN 97. Unconventional superconductivity has been deduced in CeIn3 from lI5In NQR, including spin-lattice relaxation rates (SLR), and AC-susceptibility measurements, as a function of temperature (T) between 0.05 and 100 K, and a pressure P of 2.65 GPa." A superconducting transition was found at T, = 95 mK, very much lower than the onset temperature Tonset= 0.15 K at zero resistance. No coherence peak was observed just below T, in the T-dependence plot, consistent with unconventional superconductivity. "'In NQR and ACsusceptibility data have been similarly reported for CeRhIn5, and 63CuNQR results for YbInCQ, under pre~sure.'~ CeRhIn5 showed a P-induced phase transition from antiferromagnetic (AF) ordering to a superconducting state. The studies revealed a homogeneous coexistence of these two types of orderings near the phase boundaries. The results for YbInCu4,which shows a first order valence transition at 42 K and ambient P, indicated a ferromagnetically ordered ground state after the valence transition was suppressed by P. The P-dependence of the "'In NQR parameters has been monitored at various T for CeRhIn5.'4*'5Some AC-susceptibility measurements were also de~cribed.'~ The compound underwent a superconducting transition at T, 2.1 K for P = 1.6 GPa. The Nee1 temperature TN was reduced above P = 1.23 GPa, accompanied by emergent pseudogap be ha vi0 ~ r.l~ The results at 1.6 GPa revealed that antiferromagnetism and superconductivity coexist microscopically.'5 This coexistent state was suggested to persist down to P 1.5 GPa. The superconductivity did not show any trace of gap opening in the low-lying excitations below the onset temperature 2 K, and the results indicated its unconventional characteristics. T-dependence of the "'In NQR parameters, including the SLR, from 0-40 K has been monitored for the heavy-fermion superconductor CeCoIn' (T, 2.3 K).16 Some "Co NMR data were also obtained. SLR measurements revealed that the magnetic nature was characterised by strong AF spin fluctuations in the vicinity of the quantum critical point (QCP). The anomalous T-dependence of the SLR for "'In nuclei could be well explained by the anisotropic spin-fluctuation model. AF spin fluctuations were found to be suppressed by a small magnetic field, reinforcing the view that CeCoIn5 is located close to the QCP. The effect on the Nee1 temperature TNcaused by substitution of Ir for Rh in CeRhl.,Ir,In5 (x = 0, 0.25 or 0.45) has been studied by "'In NQR, including the T-dependence of the SLR.17TNwas found to increase slightly on substitution of Ir for Rh up to x = 0.45. This resembled the behaviour in hydrostatically pressurised CeR hTn5below 1.O GPa. These measurements were extended to CeRho,51ro.51n5 and CeRhInS under pressures up to 1.6 GPa; LaRhIn5 and LaIrIn5were also used as reference

-

-

1 :Nuclear Quadrupole Resonance Spectroscopy

3

compounds.'* TNdecreased with application of P = 1.6 GPa or replacing half of Rh with Ir, probably due to an increase in bandwidth. In CeRh&-o,51n5, unconventional superconductivity set in well below TN,with T, 1 K. The "'In SLR as a function of T has been followed for Ce (Ir, Rh) 1x15,and for analogous La (Ir, Rh) In5.I9The SLR was higher by an order of magnitude for the Ce compounds, indicating strong magnetic fluctuations. CeIrIn5was located near the QCP, with quasi-2D spin fluctuations. For this compound, the SLR varied with T3below T, = 0.40 K, indicating unconventional superconductivity with a line-node gap. CeIrIn5 was much more itinerant than CeRhIn5.

-

2.2 Group 14 (Germanium-73). - 73GeNQR (and NMR) data have been obtained for a 73Ge-enrichedsample of UGe2 at ambient P and 1.3 GPa.20At the latter P, the T-dependence of the SLR from 0.01-100K demonstrated the onset of a superconducting transition at T, = 0.55 K. The lack of a coherence peak just below T,, followed by T3-like behaviour in the T-dependence plot, provided evidence for an unconventional superconducting state that coexists with the ferromagnetic state on a microscopic scale. 2.3 Group 15 (Nitrogen-14, Arsenic-75, Antimony-121 and -123, and Bismuth209). - The technology of NQR detection with particular reference to I4N nuclei has been described, and some experimental results presented.21 It has been demonstrated theoretically and experimentally that irradiation of a powder sample containing spin-1 nuclei by two of the three characteristic NQR frequencies can result in several echo signals at the third NQR frequency.22Experiments were carried out for N a N 0 2 and the organic compound RDX at 27°C. The principal echo had the same shape and time of occurrence as the echo produced after a pair of single-frequency excitations, but the other two echoes were not equivalent to any single-frequency echo. The time of occurrence and shape of these secondary echoes were determined by the correlation of the distribution in one transition frequency with the distribution in the second transition frequency. This correlation in turn was determined by the correlation between the distributions of the efg components, which was itself determined by the type and concentration of crystal defects present. Optimal conditions for observing these secondary echoes were derived. Very good agreement was found between theory and experiment. This could represent a promising method for the study of internal strains and defects in materials containing spin-1 nuclei. Transient processes observed previously in a single crystal of N a N 0 2 subjected to the pulse sequences MW-2 and MW-4, and their modifications with 180" flip angle of the pulses, have been explained theoretically in the frame of a The nature of the echo signals in the effective field of two-particle multi-pulse sequences received by phase inversion of the pulses, or by introducing an additional 180" pulse, was connected with re-focusing of the accumulated digressions of the flip angle from the ideal 180" pulse. Experimental results from powdered samples of N a N 0 2 and an organic compound at RT showed single and multiple echoes in the effective field of various pulse sequences. Multiple echoes in the envelope of the NQR signal have been obtained in a field of

4

Spectroscopic Properties of Inorganic and Organometallic Compounds

multipulse sequences for powdered 14N-containingsamples, including NaN02, at 293 K.24Echo signals were observed over a wide range of pulse rotation angles. An analogue of the magic NMR echo in solid-state NMR could be obtained under certain conditions. The pulsed spin-locking effect has been observed in 14N NQR from polycrystalline NaN02 at 297 K, using a phase coupled pulse sequence (PCPS).25The dependence of the effective relaxation time on the PCPS parameters was also investigated. This dependence and the spin-echo signal behaviour were very similar to those in a conventional pulsed spin-locking experiment. Various composite pulse sequences as used in powder NMR have been applied to the NQR of 14Nnuclei in a powdered sample of NaN02at 22°C.26 Best outcomes were achieved using the composite pulse (45)o (90)lso (164)0in the majority of cases. An experimental and theoretical study has been described of quasistationary and stationary states established in a quadrupolar spin system subjected to a chain of identical pulses that can be preceded by a preparatory pulse.27A theoretical expression was obtained for the magnetisation of the spin system that took into account off-resonance conditions. Experimental measurements on powdered samples of NaN02 and RDX at 22°C were described, and the results compared with theoretical calculations. Possible applications for the detection of N-containing explosives were discussed. T-dependence studies from 77-298 K have been reported for 75AsNQR from CO(ASF~)~.~A Three S F ~ resonances .~~ were detected at 298 K. The two lower frequency lines showed a nearly linear T-dependence with a relatively small positive T coefficient to 180 K, where the signals disappeared in the noise, and were attributed to the two AsF6 octahedra. The high frequency line had a negative T coefficient and was visible to 77 K; it was assigned to AsF3pyramids. A very short relaxation time was found for the low frequency lines, probably due to the paramagnetic Co2+ ions as efficient relaxation centres. In the related compounds Co(AsF&, Co(AsF&.2SbF3, Co(AsF6)2.2S02 and M ~ ( A s F the ~)~ signals were broadened beyond detectability by paramagnetic local fields. The T-dependence of 7 5 A NQR ~ parameters, including the SLR, from the Kondo semiconductor CeRhAs has been monitored from 0-300 K, to study the successive phase transitions found recently, gap formation and their i n t e r ~ l a y ?Some ~ 75AsNMR data were also presented. For the three well-resolved signals from the low T phase IV below 165 K, (TIT)-' showed an activation type T-dependence, suggesting a gap opening over the entire Fermi surface, in contrast with the V-shaped gap in isostructural CeNiSn and CeRhSb. The evaluated gap and bandwidth were an order of magnitude larger in CeRhAs. In phase 111, between 165 and 235 K, the NQR frequency changed discontinuously. Only one signal was detected in phase I1 at RT. Pulsed NQR measurements for 7 5 Anuclei ~ have been reported for crystalline and glassy As2S3 and As2Se3at 77 and 300 K.30,31 As a function of pulse separation, the decays of the NQR Hahn echoes following a 90"-180" pulse sequence showed damped oscillations superimposed on an exponential decay. The damped oscillations were explained in terms of indirect ( J ) coupling between two As nuclei via polarised electrons on S or Se. Values of J couplings were obtained from the periods of the oscillations and calculations of the most probable

1 :Nuclear Quadrupole Resonance Spectroscopy

5

transitions using second-order perturbation theory. The value estimated for 2J (75As-S-75As) in crystalline As2S3by this means compared well with an empirical There were insufficient experimental estimate from a value for 2J (31P-As-31P). data on 2J (X-Se-X) to make a similar empirical estimate for the Se compound. 7 5 ANQR ~ (and high field NMR) lineshapes in glassy AS& and As203have been compared before and after photodarkening (As2&)or X-ray irradiation No significant changes were found. The results were inconsistent with a microscopic model of photodarkening that involved the switching of a large number of As-chalcogen bonds. NQR experiments on 75Asnuclei, including measurement of T1 values, have been used to study local structural order in amorphous As-Se systems.33Regions were identified with As atoms bound to zero, two or three Se atoms. Bonding at lower As concentrations was governed by preferential bonding (chemical ordering) between As and Se, but at higher As concentrations was governed by both chemical ordering and statistical effects. Above 45% As, the spin-echo spectra were narrower and peaks corresponding to different numbers of As-As bonds appeared, possibly revealing As-rich small clusters formed to release local strains. The TI values suggested that the rigidity decreased dramatically for As concentrations >40%, in contradiction with the predictions of mean field theory, which thus cannot be applied to such systems. NaFe4Sb12and KFe4SbI2have been synthesised and their properties investigated by various physical techniques, including Sb NQR for the Na compound.34Five lines were observed, assigned to two transitions for 121Sband three for 123Sb,showing only one crystallographic site. Below T, (85 K), all the lines decreased sharply to zero, demonstrating the onset of ferromagnetic ordering through an increase of the internal field at the Sb site. A single crystal of CdSb has been grown, and its Zeeman Sb NQR spectra obtained at 77 and 300 K.35 The orientation of the efg about the unit-cell crystal axes was established for the Sb atoms, which are all crystallographically equivalent. Features seen previously in the 209BiNQR spectrum of a Bi4Ge3OI2single crystal were taken as an indication of the presence of ordered local magnetic fields in the compound. Experimental data necessary for the computer simulation of the NQR spectra in external magnetic fields were obtained. Four spatially different orientations of Sb-Sb bonds and the corresponding efg qzzaxes were found. 121Sband 123Sb NQR spectra and the SLR have been recorded as a function of T from 0-150 K for YbSb2 in both the normal and superconducting (T, 1.4 K) states.36Two different Sb sites were found. In the superconducting state, the SLR had an exponential T-dependence, indicating the occurrence of s-wave superconductivity. l/TIT was T-independent between 2 and 150 K in the normal state, consistent with T-independent susceptibility and almost no contribution from Yb ions. The results showed that the SLR was determined by magnetic interactions. 121Sb,123SbNQR frequencies and the SLR between 0 and 150 K have been monitored for the filled-skutterudite compound PrRu4Sb12in both the normal and superconducting (T, 1.3 K) The T-dependence of the resonance frequencies revealed an energy scheme in the cubic crystal electric field of the Pr3+ions, consistent with an energy separation of -70 K between the ground and first excited states. In the normal state, the Korringa relationship was valid.

6

Spectroscopic Properties of Inorganic and Organometallic Compounds

These results could be understood in terms of a conventional Fermi liquid. In the superconducting state, the SLR showed a distinct coherence peak just below T,, followed by an exponential decrease, showing that the compound is a typical weak-coupling s-wave conductor. This is in strong contrast with the heavyfermion superconductor PrOs4Sb12.The results highlighted the fact that the Pr-4fl derived nonmagnetic doublet plays a key role in the unconventional electronic and superconducting properties of the 0 s compound. Nuclear spin-lattice relaxation of 209Binuclei has been followed as a function of T in the range 9-300 K for Bi4Ge3OI2, where local magnetic fields of ca. 30 G had been previously detected by NQR m e a s u r e m e n t ~ . The ~ ~ , ~experimental ~ relaxation curves could be described by a single effective spin-lattice relaxation time T1*,and the T-dependence of the SLR was close to a T" law with n = 2.4-2.7 between 10 and 230 K. Nuclear spin-lattice relaxation was calculated theoretically for a single-axial crystal electric field, taking into account both quadrupolar and magnetic relaxation mechanisms. The magnetic mechanism was deduced to contribute noticeably to relaxation for T < 50 K. 2.4 Group 17 (Chlorine-35 and -37, Bromine-79 and -81 and Iodine-127). - A detailed T-dependence study of the 35ClNQR parameters from (ND4)2PtC14 has been undertaken between 12.4 and 425 K, including spin-lattice relaxation times, resonance frequencies, linewidths and integrated intensities compensated for the Curie law effect."" An order-disorder phase transition was found at 148 K. Above this T, unrestricted mobility of the ND4+ ions dominated up to ca. 350 K. At higher T, the mobility of PtC12- ions became detectable, firstly torsional oscillations and then reorientational jumps. Anomalies in the T-dependence plots were observed around 45 K, 66 K and 100 K, and explanations suggested for these. 35ClNQR spectra for N-Cl at 77 K have been recorded for a series of Na (or K) salts of N-chloroaryl sulfonamides, and for organic N,N-dichloroaryl sulfonamides, in a study of substitution effects in the phenyl ring:1 A good correlation was found in both cases between the frequencies and the frequency difference from that of the parent unsubstituted compound, although no systematic frequency variation with substituent was apparent. A new method has been demonstrated in which NQR was observed following excitation at half the resonant frequency (two-photon excitation)?2 For axially symmetric systems, two-photon NQR produced observable magnetisation only perpendicular to the R F excitation coil, necessitating a second coil for detection. If the asymmetry parameter q # 0 or a weak magnetic field was applied, magnetisation observable in the excitation coil was produced. This was shown experimentally for the 35Clresonance from a single crystal of NaC103 in the presence of a weak magnetic field. Advantages and disadvantages of the method were discussed. 35ClNQR field constants at 77 K have been obtained for the C14Sn.2POC13c0rnplex.4~Complexation was accompanied by a rearrangement of electron density distribution, shown by a decrease in frequencies for the acceptor and an increase in frequencies for the donor. The polarisabilities of the Cl atoms were also affected by complexation, increasing slightly in the donor and decreasing in the acceptor moiety.

I: Nuclear Quadrupole Resonance Spectroscopy

7

The electronic structures of some coordination complexes of SnC4, SbC15, TiC14 and NbC& have been analysed using density functional theory.44NQR spectral parameters calculated using pseudo-potential and all-electron basis states were compared with experimental values for 35Clnuclei at 77 K. Use of the central atom pseudopotential led to a significant deviation of atomic quadrupolar coupling constants from experimental values. Bonding was analysed by making use of the natural orbitals of M-Cl and M-L bonds. Donor-acceptor interactions in complexes of main group elements were described within a framework of sp-hybridisation, whereas sd-hybridisation was used for those in transition metal complexes. Two different linear correlations have been found between experimental 35ClNQR frequencies at 77 K and charges on the chlorine atoms calculated by MNDO procedures, firstly for RP(0)C12(R = C1, F, OMe, SMe, OPh or OC6H2C13-2,4,6)and secondly for R’P(0)C12( R = Me, Et, iPr, ClCH2, CF3, CH2 = CH, PhCH = CH, Ph, 4-ClCsH4, 3-ClCsH4, 4-MeCsH4, 3NO2C&t4, 2-Thienyl, 2-py, Me2N and Et2N).45Ab initio (RHF/6-31G* and MP2/6-31+ G**) calculations showed that the increased electron acceptor character of R relative to R’ led to a higher percentage of chlorine s - A 0 in LP1. Increasing steric effects did not influence the hybridisation of the Cl lone pairs in either series, in contrast with RPCl2 species. The results of ab initio calculations at the MP2/6-31G(d) level for ClPXX’ (X,X’ = Et, NMe2, OMe) and ClP(M)XX’ (M = 0,S; X = Me, OMe, X‘ = Et, OMe) have been compared with 35ClNQR data at 77 K for these compounds, and with previous calculations at the RHF/6-3 1G(d) The new calculations confirmed the non-inductive influence of heteroatoms on the geminal C1 atom in non-linear Cl-P-M groups, and agreed generally with the conclusion that abnormal correlations of 35ClNQR frequencies with different X, X’ and M were caused by P-Cl bond polarisation under the influence of the partial charge on the geminal atom. Satisfactory agreement was obtained between experimental and calculated 35ClNQR frequencies. T-dependence of the halogen NQR parameters, including the resonance frequencies, TI and T2 values, has been monitored for MeHgX (X = C1, Br or I) between 77 and 360 Phase transitions were detected at 162 K for X = C1 and 310 K for X = Br, but signals were lost for X = I before the expected phase transition at -400 K. A mechanism for the phase transitions was proposed, together with an explanation for the 35Clspin-lattice relaxation behaviour as a function of T in MeHgC1. NQR parameters, including quadrupolar coupling constants and q values, have been calculated using density functional theory (DFT), and the results compared with experimental data for halogens in several inorganic compounds and for 14N in some organic compounds.48 The most reliable values were obtained within DFT using B3LYP functional and middle 6-31G* or extended 6-311G* basis sets. The effect of the Townes-Dailey approach was also analysed, and found to cause e 5% deviation. A possible source of discrepancies between calculated and experimental results in some cases was considered to lie in the fundamentals of the method of pseudopotentials. The crystal structure of the low-T phase of 4-NH2C5H4NHSbBr4-, which undergoes a first order phase transition at 224 K, has been ascertained at 220 K, +

Spectroscopic Properties of Inorganic and Organometallic Compounds

8

and the results correlated with *lBr NQR The crystal structure of the RT phase was already known. The spectra for the low-T phase were shown to be closely related to the anion structure and H-bonds. The cations were found to be ordered, while the SbBr4- anions were incorporated into infinite polyanion chains of irregular SbBrs octahedra with two edges sharing. Both N-H groups participated in N-H---Br H-bond formation. The results were compared with those for the pyH salt, which has a different anion structure in the low-T phase, a different type of phase transition and a different H-bond scheme. 79BrNQR frequencies have been estimated using ab intio calculations at different levels, and compared with experimental data at 77 K for BrCN, BBr3 and several organic molecules.50Best agreement was found when estimating the NQR frequencies using the sum of the populations of the 13p- and 14p-components of the Br atom valence p-orbitals obtained at the RHF/6-311G(d) and particularly the RHF/631 G(d) level. Agreement was not improved by taking electron correlation into account, either partially in the B3LYP method or more fully in the MP2 method. Structure and lattice dynamics in NH4103.2H103have been studied by various physical methods, including the T-dependence of the lZ7INQR parameters between 77 K and RT.” Three lines were observed for each transition above T, = 213 K, and six lines below this T. The pressure-(P)-dependenceof the quadrupolar coupling constant and q were also obtained from analysis of results at 77 K. The phase transition was deduced to be an isostructural one connected with the destruction of bifurcated H-bonds, which became asymmetric below T,. A mechanism for the phase transition was postulated, involving proton ordering at T, accompanied by duplication of the crystal unit cell, while retaining crystal symmetry.

+

3

Transition Metals and Lanthanides

3.1 Manganese-55.- Unusual behaviour has been observed in the 55MnNQR parameters for the Mn I1 site in p-Mn metal as a function of T.52The signals suddenly disappeared above ca. 220 K, accompanied by a rapid increase in the SLR. The T-dependence of the SLR below ca. 100 K was compatible with self-consistent renormalisation theory for an itinerant nearly antiferromagnet, but the higher T behaviour was difficult to explain on this basis, and possible causes were discussed. 3.2 Cobalt-59. - Different results and conclusions have been reported from independent studies on 59C0NQR for The T-dependence of the SLR in both the normal and superconducting states (T, 4.5 K) was monitored up to 30 K.53In the normal state, the SLR was nearly proportional to T. In the superconducting state, it exhibited a coherence peak and decreased with decreasing T below 0.8 T,. The results could be understood by considering the possible effect of a small amount of magnetic moments in the Coo2 layers. Detailed comparison with the results for NaxCoOz(x = 0.75) suggested that the metallic state of the hydrated compound was closer to a ferromagnetic phase

-

9

1: Nuclear Quadrupole Resonance Spectroscopy

than that of the anhydrous species. The second investigation gave different results below T,, in that the SLR was proportional to T far below T, and no coherence peak was ob~erved.’~ The results suggested unconventional supercon4.7 K and a ductivity. Two samples were studied, NaxCo02.yH20with T, second non-superconducting material with partial extraction of the H 2 0 molecules between the C o o 2layers. The nearly ferromagnetic spin fluctuations were suggested to play a primary role in the mechanism of superconductivity in the former sample. The third report also found no coherence peak for N%.75C002.yH20below T, (3.9 K).55The SLR followed a T” dependence with n N 2.2 down to 2.0 K, but crossed over to variation with T below 1.4 K, suggesting non-s-wave superconductivity. Data for the superconducting state were most consistent with the existence of line nodes in the gap function.

-

-

3.3 Copper-63 and -65. - Various physical methods, including the T-dependence of the Cu NQR parameters at low T, have been applied to BaCu02+,, where x = 0.14.56The signal intensity decreased with decreasing T without significant line broadening, and disappeared below 2.4 K. (No signals could be detected within this T range for B ~ C U O ~The . ~ . SLR ) showed a small anomaly near 8 K followed by a slight decrease, which could be associated with short-range ordering of paramagnetic Culsclusters. The T-dependence of the 63CuSLR from 0 - ca. 150 K has been ascertained for YbZnCu4 and Y b A ~ c u , . Some ’ ~ 63CuNMR data were also reported. The SLR for YbZnCu, above 1.4 K and for YbAuCu, above 50 K were proportional to the uniform magnetic susceptibility,indicating that the correlation time of Yb spins was nearly independent of T. (TIT)-* for YbAuCu, below 50 K exhibited a prominent increase, probably associated with a decrease in the correlation time of Yb spins to the Kondo fluctuation rate. Various physical measurements on YbInCu4 have included the P-dependence of its 63CuN Q R parameters at pressures up to 1.3 GPa.58The resonance frequency increased with P from 14.1 to 14.7 MHz in the low T phase and from 14.8 to 15.3 MHz in the higher-T phases, associated mainly with unit-cell contractions. In contrast, the SLR was little affected by P. Cu N Q R spectra at 1.4 and 4.2 K have been recorded for single crystals of Sr14-xCaxCu24041 with 0 < x d 11.5.59The Cu N Q R frequency for the ladder sites at 4.2 K increased linearly with increasing x, whereas that for the non-magnetic Zhang-Rice sites in the chains did not. A detailed site assignment for the spectra, which differed from that in a previous paper, was presented. The T-dependence of the SLR for Cu nuclei in CeCu2 (Si0.98Ge0.02)2 has been monitored at various pressures.60(In the compound, AF order at TN 0.75 K coexists with superconductivity below T, 0.4 K.) At pressures exceeding 0.19 GPa, AF order was suppressed, demonstrating that the sudden emergence of A F order due to Ge doping could be ascribed to intrinsic lattice expansion. Exotic superconductivity at 0 GPa was found to evolve into a typical heavy-fermion type with a line-node gap for P 2 0.91 GPa. The relationship 1/T1T = constant was observed well below T, at P = 0 GPa, attributed not to an impurity effect but to persistence of low-lying magnetic excitations, which could be inherent to the coexistence of antiferromagnetism and superconductivity.

-

-

-

10

Spectroscopic Properties of Inorganic and Organometallic Compounds

The T-dependence of the SLR for 63Cunuclei in the quantum critical point (QCP) system CeCu5.9Auo.lhas been measured from 0.1-4.2 K.61Below 1 K, the magnetisation recovery exhibited a stable, nonexponential decay function, believed to signal the onset of 2D quantum critical fluctuations. The SLR varied with for T<1 K. The observed T-dependence was in agreement with a phenomenological model of non-Fermi liquid behaviour based on uniform susceptibility, but inconsistent with calculations based on susceptibility peaks identified via neutron scattering experiments. Possible origins of this apparent discrepancy were discussed. Cu NQR (and NMR) measurements as a function of T for CeCU6.xAUx(x = 0,O.l or 0.8) have been used to obtain information on the spin dynamics and QCP.62Fermi liquid behaviour was found for x = 0, whereas for x = 0.8 the T-dependence of the SLR was that expected for a nearly A F metal ordering at T N = 2.2 K. For x = 0.1, around the QCP, a response function of the form suggested by neutron-scattering could explain the main experimental findings. The T-dependence of the Cu NQR parameters, including the SLR up to 50 K, for CuSi03has revealed the absence of a noticeable local hyperfine magnetic field on the Cu nuclei in the A F ordered state below TN z 8 K, and considerable charge redistribution when compared with C U G ~ OThe ~ . results ~ ~ suggested a possible non-magnetic Cu+ with A F ordered oxygen surroundings, meaning the hole in the C u 0 2cell should be localised at 0 rather than Cu sites. A qualitative picture was proposed to account for the effect of Ge-Si replacement, with the main role played by 02sp hybridisation effects. CuSi03 was assumed to be a system of S = oxygen 0 2 s p holes coupled by weak 180" in-chain A F superexchange via nonmagnetic Cu+ ions, and a weak nearly 90" inter-chain ferromagnetic superexchange via nonmagnetic Si4+ions. The unusual quadrupolar SLR was attributed to fluctuations of the electric dipole moment. 63CuNQR spectra have been recorded for six Nd-doped La2-,SrxCu04(0 < x < 0.15) samples.64The spectra showed a systematic evolution with the extent of Nd and/or Sr doping, except for Lal.48Ndo.4Sro.12C~04, which gave a similar spectrum to that of the undoped insulator La2Cu04.A static stripe phase on the NQR timescale was suggested as possibly being responsible for the anomalous spectrum. Very detailed systematic 63CuNQR T-dependence studies have been reported of the spatial variation in electronic states in La2-,SrxCu04(0.04 < x < 0.16), using a 63Cuisotope-enriched polycrystalline sample.65By analysis of the extent of the frequency dependence of the SLR across the inhomogeneous linebroadening, the spatial variation in hole concentration was determined. A novel approach incorporating random positioning of Sr2+ions in the lattice enabled the entire 63Cu NQR spectrum to be fitted using a patch-by-patch distribution of spatial variation, with the patch radius as the only free parameter. The onset T of local orthorhombic lattice distortions was deduced, and in the region x 2 0.04 found to be larger than the onset T of long range structural order. Various physical techniques including Cu NQR have been used in a detailed study of the magnetic phases obtained during a topotactic chemical reaction of YBa2Cu306,5 with low-pressure water vapour.66Evidence was found that the 'empty' Cu(1) chains formed an easy water insertion channel. The NQR spec-

-

1 : Nuclear Quadrupole Resonance Spectroscopy

11

trum of the starting material transformed progressively with the insertion of H20, and disappeared completely when one H 2 0 molecule/unit cell had been added. The results were shown to be compatible with a coexistence of phases during the early stages of reaction. Even samples packed in paraffin underwent transformation of an essential part after storage for six years in the atmosphere. 63Cuand 65CuNQR spectral parameters have been measured for some textured ceramics.67Cu NQR data, including the T-dependence of TI,have been recorded for HgBa2Ca2Cu3O8+6, both above and below T, (134 Q6* Two Cu line pairs were observed above T,, corresponding to the two inequivalent Cu lattice sites. Below T,, the signals split into six line pairs. The origin of the line splitting was ascribed to the formation of magnetic moments in the CuO layers, oriented parallel to the symmetry axis of the efg, and of the order of 1000 G. Cu NQR spectra for the Cu(1)sites in four samples of E ~ B a ~ C u 3 0 (0.25 6+~ d x < 0.5) have provided evidence for a homogeneous oxygen stoichiometry in each case.69The signals were narrower than often reported in the literature, indicating high quality materials. The spectra were found to depend on both composition and preparative procedure. Results were compared with those from a 1.1SR study, and suggested that a phase-separated state was formed via intrinsic phaseseparation mechanisms, such as stripe-phase instabilities. In all the samples except the least-doped one, a high TN AF phase was found to coexist with a sizeable non-magnetic fraction. Cu NQR (and neutron diffraction) data at 4.2 K for Y b S r 2 C ~ ~ have 0 ~ +shown ~ that the compound was locally tetragonal, and no CuO chains were formed, in contrast with YBa2Cu307.70 This arose from random occupancy of oxygen along the a or b direction in the basal phase. From analysis, the reduction of T, on replacing Ba by Sr was attributed to a reduction in hole transfer from the basal CuO planes to the superconducting C u 0 2 planes. Ab initio calculations of the electronic structure, using the full-potential linearised augmented-plane-wave (FLAPW) method in the local density approximation (LDA), suggested that CuO chains were not formed because of large elastic strain, associated with the orthorhombic distortion produced by chain formation. The T-dependence of the Cu NQR spectra has been monitored for La2-,-,M,Sr,Cu04(M = Nd, Gd, Eu, Pr or Y) and La2-,BaxCu04for x = 0.125.71 The low T tetragonal (LTT) structure was stabilised below Td2for all except M = Pr. The usual NQR spectra observed for T > Td2changed to abnormally broad ones after complete wipeout below Td2,except for M = Nd, Gd or Pr. For M = Nd or Gd, wipeout continued to 1.5 K. For M = Pr with no LTT phase, the usual NQR spectrum continued to 1.5 K. The results supported a pinning model for static stripe ordering in the LTT phase. T-dependence of the SLR, spin-spin relaxation rate and Cu NQR frequency at the Cu planar sites in the normal state of YBa2Cu408has been measured at high P.72The pseudo-spin-gap temperature decreased slightly with increasing P. Pressure effects resembled carrier doping effects in increasing T, and the NQR frequency, and decreasing the spin-gap temperature. Possible mechanisms for these changes were discussed. Ni impurity spin fluctuations in YBa2(Cul-xNix)408and YBa2(C~1-~Ni~)306.92 have been studied via the T-dependence of the 63CuSLR.73The effects were found to differ

12

Spectroscopic Properties of Inorganic and Organometallic Compounds

from that of a magnetic impurity in a conventional metal, e.g. Mn or Fe in Cu, with a novel T-dependence, and possible causes were considered. Zn substitution effects in La2.,SrxCul..,Zny04 for underdoped (x = 0.10; y = 0, 0.01 or 0.02), optimally doped (x = 0.15; y = 0 or 0.02) and overdoped (x = 0.20; y = 0,0.03 or 0.06)samples have been investigated via Cu NQR between 4.2 and 300 K.74The Cu NQR signals were wiped out for Zn-substituted underdoped samples below ca. 40 K , and partially disappeared for optimally-doped materials below ca. 10 K , but not for overdoped samples. From the results, the wipeout effect was associated with Zn-induced Curie magnetism or its extended glassy charge-spin stripe formation. The main and satellite 63CuNQR signals and SLR for plane-site Cu(2) in optimally doped YBa2(Cu1-xZnx)307-6 (0 < x < 0.033; 7-6 = 6.92 - 6.95) have been studied as a function of T up to 300 K.75376 The Cu spin-lattice relaxation time was found to distribute in the broadened Cu(2)NQR spectra, in contrast with the nearly frequency-independent relaxation in slightly oxygen-deficient YBa2Cu3OY. TI for the Zn-induced satellite signals was shorter than that for the major signal, suggesting a locally enhanced magnetic correlation by Zn. The origin of the pair-breaking mechanism due to Zn impurity was discussed. The estimated exchange coupling constant due to Zn-induced local moments was too small to account for the observed decrease of T, with Zn substitution. Similar results were obtained for underdoped YBa2( C U ~ - , Z ~ , ) ~ O ~ . ~ ~ Pure YBa2C&O8is a stoichiometric, homogeneous, underdoped electronic system; nevertheless, the Zn-induced inhomogeneous magnetic response in the C u 0 2plane was more marked than that for optimally doped YBa2Cu307-6.Other results for Cu nuclei have been described in the sub-section on Group 13.13 3.4 Lanthanum-139. - The SLR for 139Lanuclei in Laz.,SrxCu04for x near the critical value 0.02, separating the A F and cluster spin glass phases, has been monitored as a function of T.77The phase diagram could hardly be defined in this region. For x N 0.016, the in-plane magnetic correlation length in the disordered (PA) phase was close to that expected for the renormalised classical regime, with spin stiffness reduced to about 40% of the value for pure La2Cu04.The PA-AF transition occurred on cooling when the in-plane magnetic correlation length reached about 150 lattice steps, close to the value in pure or very lightly doped La2Cu04.'39LaNQR relaxation data (together with '39Laand 89YNMR results) for underdoped superconductors of the LASCO (and YBCO) family have been used to extend the information on fluctuating magnetic fields in the low T range.78The data were considered to be hardly consistent with the assumption that low-energy spin excitations were due to randomly distributed 'anomalous' magnetic moments related to charge inhomogeneities. Instead the results justified an approach based on an extended t-J model including the Coulomb interaction, and in which the magnetic field fluctuations were attributed to sliding motion of vortex-antivortex orbital currents, coexisting with the d-wave superconducting state. 3.5 Praseodymium-151. - A hole-burning technique has been used to study hyperfine interactions in the NQR of 151Prnuclei from Pr3+:YA103 for both the

1 :Nuclear Quadrupole Resonance Spectroscopy

13

ground state and an electronically excited state.79The spectra depended sensitively on the relative orientation of the nuclear-spin-quantisation axes of the two electronic states. A value for the angle between the two principal axis systems was obtained, resolving discrepancies in earlier measurements.

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2 Characteristic Vibrations of Compounds of Main Group Elements BY G.DAVIDSON

1

Group1

Raman data have been reported for Li2, L& and Lig clusters in argon matrices. For Li2,the vibrational wavenumbers were: 6Li2381.2 cm-', 6Li7Li368.0 cm-', 7Li2354.0 crn-'; Li4( D 2 h ) 'Li4 355.2 cm-' (a,), 252.5 cm-' (bl,), 7Li4326.8 cm-' (a,); Lig(Td)v1 (al)327.1 cm-' (6Li),295.3 cm-' (7Li),v6 (t2)320.4 cm-' (6Li),298.9 cm-' (7Li).' Ab initio calculations of the vibrational wavenumbers for CH2CHOLi gave data which could be compared with experimental IR and Raman values of aggregates containing this unit bound to "BuLi2 The Raman and IR spectra of LiMn204 (with 6Li/'Li isotopic shifts) showed that vLi04modes lay in the range 350 - 400 An alternative assignment of vLi-0 (525 cm-') was proposed from IR data for LiMn204and LiM,Mnz-,04 (whereM = Mgor Cu).' A detailed Raman study of Li2B407crystals gave vibrational assignments based on isotopic (6LipLi; loB/''B) shifts6 IR spectra of Li2O.B2O3.Al2O3 glasses included bands at 250 cm-' and 480 cm-l due to v L i 0 motion^.^ The far-IR spectrum of LiFeSi206gave a band assigned to mixed vLiO/vFeO in the range 300 - 330 crn-'.* IR assignments have been proposed for vM-X bands in alkali halide/H2 systems in neon matrices, e.g. for LiCl, v7LiCl is at 623.2 cm-' for the monomer, 502 cm-' for the dimer.9 The Raman spectrum of micro-crystallites of LiBr contained too many bands for the suggested symmetry of DSh.lo The clusters Na2,Na4 and Naghave been isolated in argon matrices at 15K and characterised by Raman spectroscopy. Assignments (based on DFT calculations) were proposed as follows: Na2,v (0,) 160.0 cm-'; Na4v1 (a,) 164.0 cm-', v2 (a,) 54.2 cm-', v3 (b3,) 105.4 cm-'. The assignments for the tetramer were consistent with a rhombic, D2h,structure. Data for Nas suggested a Td geometry (face-capped tetrahedron)." Adsorption of C 0 2 on thin potassium layers supported on Cu(111) gave a far-IR band at 232 cm-', due to v K - 0 of K2C204.'2 The IR spectra of K f containing mixed-layer minerals include a band in the range 71 - 89 cm-', due to Kf ion motion^.'^ Spectroscopic Properties of Inorganic and Organometallic Compounds, Volume 37 0The Royal Society of Chemistry, 2005 17

Spectroscopic Properties of Inorganic and Organometallic Compounds

18

Ab initio calculated wavenumbers have been reported for MOH and MOH+, where M = Rb, Cs or Fr.14 The Raman spectrum of CsGaSe3includes a band at 187 cm-', assigned as vCs-Se, together with vSeSe at 238 cm-l, and vGaSe at 226,259 and 272 cm".'' 2

Group2

High-resolution IR emission spectroscopy for BeH and BeD gave we values of 2061.416(3)cm-' and 1529.956(3)cm-' respectively.16Similar data for BeH2and BeD2gave v3 (a,)of 2178.8659(2)cm-' and 1689.6788(3)cm-' respectively, with a corresponding 0 3 3 value of 2255.155(11)cm-I for BeH2." The Raman spectra of beryllium-doped cubic boron nitride crystals included a band at 535 cm-' due to a Be-impurity-induced vibration." Raman spectra of Be-implanted GaN epilayers included features at 168 and 199 cm-' which have been assigned tentatively as Be-related local vibrational modes.19 The IR and Raman spectra of [Be40(C03)6]6-show two bands in the region of 480 cm-1 ascribed to Be40 motions.20 IR spectra of MgSi03 at high pressures contain low-wavenumber bands associated with the stretching of weak Mg-0 bonds.21IR and Raman spectra gave assignments to vMgO, vAlO, vSi0 and 6OSiO modes in polygorskite and sepiolite minerals?2Molecular dynamics calculations on [Mg3Al(OH)8]C1.3H20 showed that experimental IR bands at 145, 180 and 250 cm-' were due to Mg vibration in the c direction, A1 vibration in the c direction and Mg/Al vibrations in the ab plane re~pectively.~~ Several Raman bands observed below 300 cm-' for Ca(SCN)2 and Ca(SCN)2.2H20are associated with vCaN and vCaS motions.24The Raman spectra of (Srl-,Ca,)Bi2Ta209ceramics included bands at 28.7 and 58 cm-', related to motions of the calcium ions.25 Photofragmentation spectra of Sr+(CO)are consistent with the formation of Sr+(OC),with vSr-0 near 200 cm-'.26 The Raman spectra of barium-doped silicon clathrates (Ba8Si46, Ba6.6Si46) give bands below 100 cm-' due to motions of the barium in the silicon cages.27 High-pressure Raman spectra (to 25.6 GPa) of BaFCl showed that phase transitions occurred at 10.8 and 21.1 GPa.28Variable-temperature Raman studies of (Me4N)2BaC14 revealed phase transitions at 369.7 K and 41 1.3 K.29 3

Group13

3.1 Boron. - The sodium salt of (1) shows vB-H at 2503 cm-'. This is unexpectedly low, as the potassium salt gives a value of 2554 ~ m - ' . ~ ' Thermal phase transitions of polycrystalline LiBH4 were followed by Raman spectroscopy in the range 295 - 412 K (vBH).~'High-pressure Raman data for H3N.BH3produced evidence for a di-hydrogen bond, with two pressure-induced phase transition^.^^ Vibrational wavenumbers were calculated by ab initio methods for SiH4-BH3-BH3(hydrogen-bridged, with Si-H-B bond).33

2: Characteristic Vibrations of Compounds of Main Group Elements

19

The high-pressure Raman spectra (to 131 GPa) of decaborane, BloH14,gave evidence for structural phase transitions near 50 and 100 GPa.34 A report has appeared on the preparation of OCBBCO, believed to have B=B bonding character. IR bands were assigned as follows: YaSCO (a,)2014.2 1086.1 cm-', 8aSBCO (xu) 517.1 ~ m - ' Vibrational .~~ wavenumcm-', YaSBC (q) bers were calculated by ab initio methods for B(BX2)3.C0,where X = F, C1, Br or 1.36 Calculated vibrational modes for LiBC were in good agreement with experiment, e.g. YB-Cnear 1200 ~ m - ' The . ~ ~Raman spectra of 'bamboo-shaped' BCN nanotubes were used to establish the nature of the hybridi~ation.~' Characteristic IR and Raman bands were reported for amorphous B/C/N materials formed by a sol-gel process from B3N3H3C13 and Me&-NCN-SiMe3.39Raman spectroscopy shows that a-B4Cis converted to h-BCN films by evaporation with N2ion-beam assistance.4' Ab initio calculations of vibrational wavenumbers have been reported for C2H5B3, i.e. 1,5-dicarba-closo-pentaborane(5)P'IR and Raman spectra were reported and assigned for the caesium salts of closo-[CB11H12]- and nido[CB1OH&, based on molecular orbital calculations and normal coordinate Ab initio calculations gave predicated IR and Raman spectra for the heterofullerene C48B12.~~ Matrix-IR data were reported for BCO, one of the reaction products of laser-ablated B atoms and CO. Assignments were based on isotopic shifts and ab initio calculations - Table 1. Bands were also seen due to OCBBC0.44A number of vibrational assignments were proposed from the IR and Raman spectra of (CF3)3BC0,including YB-CO at 357 ~ m - ' . ~ ~ Semi-empirical calculations were carried out on a range of organosilylboranes. Calculated values for YBSi were in the range 480 - 650 cm-', e.g. for Me3SiB(NMe2)2 the calculated value of 520 cm- ' compared with an experimental one of 486 cm-1.46 Table 1

Skeletal mode assignments for BCO (lcm-')

Y1

2007.3 1148.1 494.8

y2 V3

1956.5 1144.7 481.3

1975.9 1130.0 490.7

2002.6 1114.1 491.3

1952.2 1109.8 477.9

1970.7 1096.5 487.2

20

Spectroscopic Properties of Inorganic and Organometallic Compounds

The FTIR spectrum of a cubic BN film prepared by physical vapour deposition included a band at 1006.3 cm-'.. This is consistent with a very low level of internal stress in the film.47Ab initio calculations were reported for BN singlewalled n a n o t u b e ~The . ~ ~ Raman spectra of such nanotubes are dominated by an e2gmode near 1360 cm-' - the exact wavenumber depending upon the temperature of deposition."' The IR spectra of BN multi-walled nanotubes show characteristic YBNmodes at 800 and 1372 cm-l.so Raman spectroscopy was used to characterise amorphous boron nanoparticles and BN encapsulating boron 'nanopeanuts'.sl Ab initio calculations gave vibrational wavenumbers for borazine cyclacene systems, (BN)n,where n = 4 - 12.52 The IR spectra of [C12BNPC12NPCl3]2 and [Br2BNPCl3I2included v,,BNP at 1159, 1138 cm-' respectively, and v,BNP at 942, 910 cm-' respectively. The former also shows YasPNP at 1330 c111-l.~~ Matrix-IR evidence was obtained for the formation of a range of novel species by the reaction of boron atoms or clusters with NO in argon matrices. These included NBO, BNBO, OBNNO, BBNO and BBBNO. Isotopic shifts gave assignments, e.g. for NBO, Yas is at 897.4 crn-', and for BNBBO, YBB is at 1138 cm-' (both values for the 14N,'lB, l 6 0 form).54 Thin BN films prepared by CVD (with B(NEt2)3precursor) on Si(100)show an IR band due to h-BN near 1360 c111-I.~'A high-resolution FTIR study has been reported for the 'vg fundamental of loB314N3'H6, taking into account resonance effects with the combination Y ~ +O ~ ~ 7 . ~ ~ has a The Raman spectrum of the adduct Me2HN.(CF3)2BOB(CF3)2.NHMe2 band due to v,BOB at 902 ~ m - ' The . ~ ~IR and Raman spectra of M7[Si04][B03] CN, where M = Sr or Ba, contain features confirming the presence of B033-, sio44- and CN- ions.58 Raman spectroscopy was used to characterise the structures of xB203.(1-x)B2S3glasses, where 0 5 x I; There have been several Raman studies relating to the structures of sodium borate glasses."-62The IR spectra of Na20-B203-Si02 and Al2O3-Na2O-B2O3Si02glasses contain characteristic B203and Si02bands.63The Raman spectra of [( 1-x)Cs20.xLi20]-B203 glasses show significant changes in pentaborate, dipentaborate and chain-type metaborate features with changing x.64 The IR spectra of samples in the Si02-Na20-M0systems, where M = Mg, Ca, IR Sr, Ba or Zn, all include characteristic bands of B03, B 0 4 and Si04 data for polyborate ions formed in saturated aqueous solutions by dissolving 2Mg0.2B203.MgC12.14H20 in the presence of MgC12include bands at 515 cm-' and 550 (due to B(OH)4-/B20(OH)62-),630 cm-' (B303(0H)4-/B303(OH)52-) cm-' (B405(OH)52-).66 Raman spectra of B203-Ca0glasses were used to probe variations in the borate structural framework with c o m p ~ s i t i o n . ~ ~ The IR spectra of Fe203-Li20-B203-Mo03 glasses contained features due to both B 0 3and B 0 4 groups.68IR spectroscopy was used to determine the proportion of B 0 4 units as a function of CuO concentration in the xCu0.(50x)PbOSOB203 Raman and IR spectra of glasses in the system La2O3MgO-B203gave assignments to a range of vB-0, YO-B-0and YB-0-B mode^.^" The FTIR spectra of Nd3+-doped glasses in the system PbO-Bi203-B203

2: Characteristic Vibrations of Compounds of Main Group Elements

21

system showed features from B03, B04, P b 0 4and Bi03units.71Raman spectroscopy was used to characterise the structures of glasses in the Sb203-B203system in terms of B 0 4 and boroxol ring modes.72IR spectroscopy was used to confirm structural relationships in BiZ03-B203 and Bi203-B203-Pb0glasses.73 Evidence was found from IR data for trigonal, BS3, coordination in H2S+ B2S3+ GeS2, with some BS4 units being formed at high GeS2 concentrat i o n ~ The . ~ ~ IR and Raman spectra of glasses zAgI + (l-z)[O.525Ag2S + 0.475(0.5B2S3+ 0.5SiS2)],where 0 s z 5 0.4,gave evidence for [BS4/2]- tetrahedral, B3S6six-membered rings and [BS3,2]trigonal units.75 The Raman spectrum of NaBF4in dimethylformamide solution suggested the . ~b~initio calculations have been formation of Na+BF4- contact i ~ n - p a i r s A reported for B4C14,including predicted vibrational wave number^.^^ 3.2 Aluminium. - There is matrix-IR evidence for the new aluminium(II1) hydrides, HAlFCl, HAlFBr and HAlClBr, together with the mixed monomeric halides AlX2Y (X, Y = F, C1, Br), from reactions of AlF/AlCl and HCl/HBr. Vibrational assignments included vA1-H at 2005 cm-' for HAlFC1, and vA1-D at 1437.9 cm-' for DAlFC1.78Skeletal mode assignments were proposed from the matrix-TR spectra of Cl(H)AlCCH and Cl(D)AlCCD - Table 2.79

P' \

Matrix-IR data were reported and assigned for Cp*AIH* and its isotopic variants - Table 3.*' The IR spectrum of (2), where Ar = C6H3iPr2-2,6,includes vAlH at 1730 cm-' from the AlH3 unit.*' The solvent-free dimer [Li(tacn)AlH&, where Htacn = 1,4-di-isopropyl-l,4,7-triaza-cyclononane, has vAlH as a broad IR band at 1707 cm-'.** Laser-ablated A1 atoms and H2 react to give a range of matrix-trapped aluminium hydrides. In addition to AlH, AlH, and AIH3, evidence was found for Al2H2,A12H4(bands at 1838.4 and 747 cm-') and dibridged

Table 2

Selected vibrational assignments for C1( H)AIC2H (/cm-')

Cl( H ) A l C 2 H

CI(D)AlC?D

Assignment

1952.2 67 1.4 6 15.9

1419.3 629.0 541.9 466.4 3 80.5

vAI-H GHALCI VA1-C vAI-CI pA1-H

505.8

49 1.4

Spectroscopic Properties of Inorganic and Organometallic Compounds

22

Vibrational assignmentsfor Cp*A1H2(/em-')

Table 3 Cp*AIH,

Cp*AIDz

Assignment

1801.5 1773.7 864.6 588.7 464.1

1304.4 1296.3 645.1 461.8

V,,Al-H v,Al-H 6AlH2 A1H2wag VA1-Cp"

~~

-

Table 4

Vibrational assignmentsfor dibridged A12H6 (lcrn-')

Table 5

Vibrational assignments for [ M ( D M S 0 ) J 3 + (/em-')

M =

A1

Ga

In

VsM06 VasMO6

465 540

49 1 495

444 440

A12H6(assignments summarised in Table 4).83784 High-pressure Raman data for AIB2 (to 40 GPa) gave no evidence for any pressure-induced structural phase transitions." The FTIR spectrum of AlN thin films includes bands at 612 and 672 cm-' due to Al-N vibrations.86The Raman spectrum of AlGaSN layers includes vA1-N bands at 449,500 and 650 c111-l.~~ The IR and Raman spectra of [M(DMSO)6]3+,where M = Al, Ga or In, gave the assignments to v M 0 6 modes listed in Table 5.88 Calculated vibrational wavenumbers for alumino-silicate ring structures were used to analyse experimental data.89FTIR data were used to characterise the structure of the aluminium Lewis-site in alkali metal-exchanged P-ze~lites.~' Assignments to v M - 0 (M = Al, Ga, Si, Ge) modes were proposed from FTIR spectra of a range of mullitetype c o r n p o ~ n d s . ~ ~ The Raman spectra of Rul-,A1,Si2GdCu208,where x = 0.05,0.1,0.15,included a feature near 550 cm-', attributed to an Al-induced al,-like apical oxygen mode.92IR and Raman spectra were used to characterise a wide range of samples from the system Na20-Ca0-A1203-P20s-Si02.93 The Raman spectra of Eu203MgO-A1203-Na20-Si02 glasses showed a broad band at 790 cm-' due to A1-0 stretching, with the aluminium in four-fold c ~ o r d i n a t i o n . ~ ~ IR and Raman spectra have been reported for isolated [AlFSl2- (as the salt) and assigned under D 3 h symmetry - Table 6.95Fluoroaluminates "Me4] dissolve in NaF-KF or LiF-NaF-KF eutectics to form AlF63-. Solidified melts +

23

2: Characteristic Vibrations of Compounds of Main Group Elements

Table 6

Vibrational assignments for [AEF5]'- (/cm-') Raman

I.R. 563 464 60 1 3 54 675 374 117 322

644 117

show Raman bands for this species at 561 crn-' (vl),391 crn-' (v2)and 328 cm-' The dimer [Cl2A1NPCl3l2shows vA1Cl2 at 441 and 404 ern-', with YP= N at 1160 cm-' and vPC13at 556 and 4 8 0 ~ m - l . ~ ~

( ~ 5 ) . ~ ~

3.3 Gallium. - The IR spectrum of Et3P.GaHC12 includes a band due to vGaH at 1930 ~ m - ' The . ~ ~Raman spectrum of Ga2H2in an argon matrix at 12K has a band at 176.2 cm-', assigned as involving both GHGaH and vGa . . . G a for the unit (3).99 The IR spectrum of (4) has vGaH at 1769 cm-', while ( 5 )shows vInH at 1632 cm-'.'OO

I-

24

Spectroscopic Properties of Inorganic and Organometallic Compounds

Dimeric [Me2GaOCy12,where Cy = c-CbH11, has Ci skeletal symmetry, and hence the mutual exclusion rule applies. vGaO bands are seen at 490 and 425 cm-' in the IR spectrum and at 505 and 442 cm-' in the Raman spectrum. Bands due to vGaC2 are at 591, 532 cm-' (IR), 588, 540 cm-I (Raman). For [In(Me21n(OCy)2)3],vInO bands were seen at 423 and 393 cm-' in the IR."' Characteristic GaN modes were seen in the Raman spectra of GaN nucleation layers and free-standing layers on oxidised silicon substrates.102Micro-Raman spectra were recorded for bulk GaN samples grown by a Na-Ga melt technique, and used to give structural chara~terisation.''~ A Raman band due to a GaN (e2)mode was seen at 566 cm-I for epitaxially laterally overgrown GaN films on a Si(111) substrate.'@' Raman spectroscopy was used to study the effects of plasma-induced damage to n-type GaN, e.g. defect peaks at 300 and 360 ~r"'.''~ The IR spectrum of GaN:Mg under hydrogen has vNH at 3125 cm-'.Io6 The Raman spectra of GaNl.,P, alloys show bands due to G a P features at 256, 314,377 and 428 cm-' Raman data for aqueous solutions of gallium(II1) perchlorate include Ga(OH2):+ bands: v1 (al,) 526 cm-', v2 (e,) 430 cm-' and v5 (t2J 328 cm-'.lo8 Thermally-induced phase transitions in SrO- and MgO-doped LaGa03 were followed by Raman spectroscopy. Characteristic new features in the doped crystals were at 520,750 and 810 cm-l.lo9 Gallium-loaded catalyst samples, Ga-ZSM-5, show vOH of Ga-OH units at 3699 cm-', probably as part of Ga2(0H),0~~x."o The complex (C2N2H10)2[Ga2(C204)2(HP04)3].H20 shows bands due to G a - 0 modes at 1152, 1062,600 cm-' (IR) and 1078,600,388 cm-' (Raman)."' The Raman spectra of MI1Ga2X4,where X = S or Se, show characteristic modes at approx. 280 and 360 cm-I (S),approx. 185 cm-I (Se).'12Raman spectra of MS-Ga2S3systems (M = Ca, Sr or Ba) contain typical Gas4bands.113Raman spectroscopy was also used to probe the structure of Er-doped (GeS2)x(Ga2S3)100.x, where x = 75,80,85 or 90,in terms of Gas4 and GeS4 The high-pressure Raman spectrum of E-GaSe showed a transition to the y-form near 29.2 GPa.'15 Similar experiments on CdGa2Se4 showed a first order phase change at 20.2 GPa.I16 The open-framework gallium selenide, [Ga4Se7(en)2]2-gave several Raman bands in the range 350 - 100 cm-' due to GaSe4 and GaSe3N units.117 3.4 Indium. - High-pressure Raman data for MIn2S4,where M = Mn, C D or Mg, gave evidence for phase changes at 7.2 GPa (Mn), 9.3 GPa (Cd) and 12 GPa (Mg).'l8 IR and Raman spectra of N2H6[InF4(H20)]2showed that the anion structure contains InF2F4,20-entities."' Raman spectra, supplemented by ab initio calculations, on liquid InC13-EMIC (where EMIC = 1-ethyl-3-methyimidazolium dichloride) confirm that InC14- is the predominant indium-containing species present. 12' 3.5

Thallium. - The solid complex cation [Tl(enkCNI2+ gives a band due to

2: Characteristic Vibrations of Compounds of Main Group Elements

25

vT1-C at 460.3 cm-I, due to the symmetric stretch between T1 and a bridging cyanide group.'21The Raman spectra of bromothallate(II1) salts of pyridinium cations gave evidence for TlBr4- and T1Br52-species.'22

4

Group14

4.1 Carbon. - Semi-empirical PM3 m.0. calculations on C2$+ gave predicted vibrational wavenumbers for the D3 ground Raman data suggest the formation of a solid phase constructed of linked C20 d 0 d e ~ a h e d r a . lDFT ~~ calculations have given predicted vibrational wavenumbers for carbon nanotubes (CNT) based on C24H12, C4gH24 and C96H24 units.'25 A b initio 111.0. calculations have given vibrational wavenumbers for C34BN;'26 c360;127-8 c4gx2 (X = B, N).'29 A novel azafullerene, C48N12, has been reported, with characteristic IR bands at 461.5,568.4,579.3,1236.1 and 1338.9 ~m-'.'~'Therehave been several ab initio and DFT calculations of vibrational wavenumbers for this specie^.^^'-^ An ab initio calculation also gave vibrational wavenumbers for c50x2, where X = H or F.'36 IR and Raman data have been reported for the Cs9N+carbocation. The ag(2) global breathing mode was seen in the Raman spectrum at 1467 cm-' (resonance enhanced by 488 nm excitation). The decreased symmetry compared to c 6 0 led to the appearance of many more bands.'37 The IR spectrum of the most stable isomer of C59H3N was calculated by ab initio methods.'38 The Raman spectrum of C60containing carbon isotopes in natural abundances suggest that isotopic perturbations are not an important source of silent-mode Raman activity.'39 Raman-active ag modes dominate the Raman spectra of potassium-doped c 6 0 thin films.'40FTIR and Raman spectroscopy was used to follow changes induced in C60 by He+ bombardment. A low radiation dose gives oligomers, while higher radiation doses produce amorphous ~ a r b o n . ' ~IR ' - ~and Raman spectra were used to characterise carbon clusters formed by laser irradiation of pure c 6 0 and diamond grains.143 The IR and Raman spectra of quasi-one-dimensional polymeric RbC60gave evidence on the temperature dependence of intramolecular c 6 0 modes.'44The IR spectrum of a linear c 6 0 polymer has been reported and compared to that for orthorhombic Rb+C60-polymer. The striking differences were due to the charge on the c 6 0 IR data were reported for ( c 6 0 - ) 2 and ( c 7 0 - ) 2 in crystalline complexe~.'~~ High-pressure Raman data for c6Os16 showed polymerisation occurred similarly to c 6 0 itself. Sg ring modes disappear at high pressure - suggesting ring disruption and the formation of covalent C-S Raman data were used to follow the structural effects of C60polymerisation above 9 GPa and at temperatures up to 830 K.'48The influence of thermal annealing (at 393,453 and 473 K) on the structure of c 6 0 films was followed by Raman spectroscopy. New bands appeared at 934,1592 and 1685 cm-' on annealing.'49 Characteristic Raman features were reported for fullerene peapods, i.e.

26

Spectroscopic Properties of Inorganic and Organometallic Compounds

C60@SWCNT (single walled carbon nanotubes), and for DWCNT (double walled CNT) formed by heating the former.15oSeveral other papers describe Raman studies on fullerene peapods, with c 6 0 encapsulated in SWCNT.'5'-4 Raman data have been reported for Ca3C70,Sr3C70and Sr9C70- the tangential mode shows a continuous downshift with increasing reduction of the fullerene~.'~~ Raman spectroscopy was used to characterise amorphous carbon (a-C) films prepared by shielded arc ion ~ 1 a t i n g .Vibrational l~~ studies have been made of the structural characteristics of nitrogenated amorphous carbon (N:ta-C) films.157Raman spectra of ta-C films was used to estimate the fraction of sp3 bonded atoms, and its dependence on the method of f0rmati0n.l~~ The Raman spectra of carbon films deposited on glass and stainless steel substrates by plasma-based ion implantation show that they are in fact DLC (diamond-like carbon) films.159The Raman spectra of carbon nanostructures formed by pulsed-laser deposition on a silicon substrate include a characteristic, but weak and broad, band at 1150 cm-'.160 The Raman spectra of carbon films formed by mass-selected ion-beam deposition at 800°C show that bonding largely involves sp3 hybridisation.16' The Raman spectra of nano-structured carbon films formed by using ammoniacontaining feed gas suggested that both graphite-like and glassy-carbon-like units were present.'62Raman spectroscopy was used to characterise amorphous carbon modified by iron.163 IR data for hydrogenated amorphous carbon (HAC) deposits prepared in the presence of deuterium include features near 2175 cm-' due to YCD, Raman spectroscopy was used to characterise hydrogenated amorphous carbon (a-C:H) and nitrided amorphous carbon (a-C:N) films on quartz s u b ~ t r a t e s . ' ~ ~ FTIR spectroscopy was used to characterise a-C:F films prepared by means of microwave electron cyclotron resonance plasma-enhanced CVD.'66Highly fluorinated C,F samples, where 1 < x < 2, show Raman features consistent with the presence of discrete C F and C2Fphases.'67 Adsorption of hydrogen on to 13Cdiamond produced by high-temperature, high-pressure synthesis gave IR bands due to YC-H at 3107 and 3098 cm-l.16' There is Raman evidence (band at 1332 cm-') for the formation of diamond by the reduction of C02 at low temperatures by metallic ~ 0 d i u m .Raman l ~ ~ scattering by diamond has been proposed as a pressure sensor for gem anvil cells.'70 Raman spectroscopy was used to study the effects on the structure of diamond of shock stresses of 45 GPa. Splitting of the degeneracy of the triply-degenerate mode was The DRIFT spectrum of an oxidised diamond (100) surface showed a Y C = 0 band at 1731 c111-l.l~~ High-pressure Raman spectra of graphite (to 24 GPa) revealed a phase transition near 18 GPa), but no diamond was detected as a result of this change.'73The Raman spectrum of graphite fluorinated at high temperature (380°C) gave evidence for a fluorinated phase containing planar, sp2-bonded,1 a ~ e r s . l ~ ~ Raman spectroscopy was used to study diamond-like carbon (DLC)films on a glass sustrate (prepared by using a high-energy-density plasma gun)."5 The structural effects of annealing DLC films in nitrogen were followed by Raman

2: Characteristic Vibrations of Compounds of Main Group Elements

27

spectroscopy (new bands were seen at 928, 968 and 2324 ~ m - ' ) . 'The ~ ~ Raman spectra of DLC films doped with N showed an increasing sp2bonding fraction with increased nitrogen ~ 0 n t e n t . A l ~DLC ~ coating modified with Ca/O compounds showed characteristic bands for sp2 hybridised ordered regions.17*Several other reports have been made of Raman spectroscopic studies of DLC films.179-182 The Raman spectra of carbon onions showed new features at 1100, 861,700, 450 and 250 cm-'. The spectrum was analysed by considering the effects of the curvature of 'graphene' planes by comparison with the graphite s t r ~ c t u r e . ' ~ ~ The Raman spectra of thin layers of SWCNT show a great increase in the intensity of the D-band (1320 - 1340 cm-') - ascribed to disorder effects.ls4 Raman spectra were reported for ropes of SWCNT grown by the HiPCO process - some samples showed a significant fraction of tubes with a diameter <1 n111.I~~ Resonance Raman data for SWCNT polymerised at high temperature and pressure gave evidence for sp3C-C bonds linking the individual tubes.'86 Raman spectroscopy was used to characterise K +-intercalation species of SWCNT ropes - especially two stable states, KC27 and KC, (x < 9).lg7Raman bands were reported and analysed for pristine and K+-intercalated HiPCO SWCNT.'88 Raman data were given for thin bundles of SWCNT suspended between metal blocks deposited on a silicon The Raman spectrum of ozonised SWCNT gave evidence for the formation of COOH groups at the tube surface (vC = 0 1708 cm-', vO-H 3410 cm-l).19' SWCNT produced by arc discharge in a bowl-like cathode gave Raman data showing that they had fewer structural defects than those produced by conventional method^.'^' Raman spectra showed that SWCNT produced with an Y/Ni catalyst had a diameter distribution from 0.79 to 1.76 nm, with a maximum at about 1.45 n111.l~~ The Raman spectra of SWCNT, diameter 0.4nm., grown in channels of AlP04-5 crystals suggested that only two types of nanotubes (with different chiralities, ((5.0),(4,2)))were A large number of other reports described the use of vibrational spectroscopy to study SWCNT.194-220 Raman scattering has been reported for double-walled carbon nanotubes, DWCNT. The wavenumbers for tangential displacement modes were downshifted by about 7 cm-' for the secondary (interior) tube compared to the larger primary (exterior) tube.221The Raman spectra of DWCNT gave a calculated interlayer distance in the range 0.335 - 0.42 nm. Note that the D-band is at 1270 cm-' for SWCNT, 1285 cm-' for MWCNT (multiwalled carbon nanotubes) but 1260 cm-' for DWCNT.222Several other papers give details of Raman data for DWCNT.223-7 Low-wavenumber Raman data have been reported for MWCNT. These were assigned to radial breathing modes of the individual walls coupled through van der Waals interaction between adjacent concentric walls.228Raman spectroscopy was used to characterise structures of highly-graphitised MWCNT (inner diameter approx. 1 nm.) prepared by hydrogen-arc discharge.229 Raman spectra of MWCNT show that the G-band modes are composed of G-band modes from the innermost tube and a graphite-like mode from the outer ~ylinders.2~' Raman spectroscopy was used to study the structural effects on

28

Spectroscopic Properties of Inorganic and Organometallic Compounds

MWCNT's of treating them with supercritical water.231 DFT calculations have been made of vibrational wavenumbers for 5 crystalline C3N4 phases. Significant differences were predicted - suggesting that IR and Raman spectroscopies will be good techniques for differentiating between these phases.232The FTIR spectrum of an amorphous nitrogen-rich carbon nitride, C3N4+,,where 0.5 < x < 0.8, shows mainly C3N3 rings, with sp2 hybridisat i ~ n .The ~ ~IR~ spectrum of electrodeposited graphite-like CN, films also contains bands due to C3N3cyclic The IR and Raman spectra of CN, films prepared by nitrogen-ion-beam assisted pulsed laser ablation of graphite show that a C3N4 phase was produced at a high nitrogen ion c ~ r r e n t . 2a-CN, ~ ~ films formed by electron-cyclotron resonance plasma-enhanced CVD from cyanogen bromide were characterised by Raman spectroscopy (especially a band near 1300 cm-', due to sp3hybridised carbon nitride).236 The IR and Raman spectra of CN, films produced at various arc currents by a vacuum cathode arc method were used to probe the number of CC bonds and proportions of sp2and sp3CN ~ n i t s . Numerous 2~~ other reports have been made of IR and Raman studies of amorphous carbon nitride A high-resolution study of the C D radical g2 ground state) by laser magnetic resonance gave values for vo of 2032.03360(18) cm-', and mexeof 34.72785(58) cm-l

251

Ab initio calculations gave predicted vibrational wavenumbers for MNCH+ . . . HLi (M = Li or Na) and XCCH . . . HLi (X = NC, C1, F or H).252Similar results were reported for the formyl (HCO) and isoformyl (COH) radical species.253 Step-scan FTIR gave experimental evidence for the formyl radical (HCO) in zeolite NaY at room temperature, with vC= 0 at 1847 cm-' (1807 cm-' for the 13Cform).254 A high-resolution study of HCBr gave band centres for v2 at 1117.70(6)cm-' and v3 at 676.4436(25) cm-1.255Transient Raman data were reported for the radicals CHBr2 (showing v,CBr2 603 cm-', vBrCBr 186 cm-') and CHBrCl (vCCl829 cm-', vCBr 643 cm-', GClCBr 236 ~ m - ' ) . ~ ' ~ A high-resolution FTIR study of HCF3 gave values for v6 507.822011(42) cm-', 2v6 1014.541504(46) cm-' and 036 507.66743 ~ m - ' . ~ Similar ~ ~ - * experiments on HC35C13gave v1 at 3032.92642(25)~ m - ' . ~ ~ ~ IR spectroscopy at high pressures gave evidence for a phase transition near 6 GPa for HCC13 that had previously been postulated from Raman studies.260 High-pressure IR and Raman spectra also gave evidence for phase transitions for HC13.261 Band centres were measured from high resolution FTIR spectra of CH2DF as follows: v3 1465.477458 cm-', v4 1364.168783(32)?62 Similar measurements on CH235C12gave v4 at 283.1877(2) and on CD235C12v3 690.6735(2)cm-' and v4 730.2146(1)c 1 ~ 1 - lAb . ~ ~initio ~ calculations gave vibrational wavenumbers for CH2C12,CHDCl2 and CD2C12.265 IR data were reported for the anion complexes X-.CH4, where X = F or Br. They were consistent with C3"structures, with X- hydrogen-bonded to CH4via a single C-H bond.266DFT calculations gave predicted vibrational wavenumbers

2: Characteristic Vibrations of Compounds of Main Group Elements

29

for (CH),, where n = 4,6,8,10 and 20.267Raman date were reported and assigned for cyclohexamantane, C26H30 - effectively a nanometer-sized diamond.268 A high-resolution study has been carried out on v5 of cyanogens, NCCN and several of its i s o t ~ p o m e r sThe .~~~ IR spectrum of the NCCN+ cation in a neon ~' matrix at 5 K showed that the a,,+stretching mode was at 1799.5 & 1 ~ r n - ' . ~IR spectra of photolysed matrix-isolated cyanoacetyl or cyanoacetylene gave evidence for the formation of HCCNC (3328, 2213, 2033 cm-l), HNCCC (3562, 2205, 1906 cm-') and CCNCH (3277, 2102, 1920 cm-') from the former, NCCCNC (2287,2204,2045 cm-'), CNCCNC (2115,1291 cm-') and CCCNCN (2275, 2219, 1927 cm-') from the latter.27' Ah initio calculations of vibrational wavenumbers have been carried out for HCC-X, where X = -NCO, -OCN, -CNO and -ONC?72 A high-resolution (tunable diode laser) IR study of fluoroketene, F(H)C = C = 0,showed that the band origin of v2was at 2147.82693 Laser-ablation of C/Si/Ge rods, with trapping of the products in an argon matrix at 10K, produced linear GeC3Si,for which v1(a,CC stretch) is at 1939.0 cm- 1.274 TRIR emission spectroscopy gave evidence for the cyanovinyl radical, [H2C=C-C=N]', with bands due to vCN at 2563 & 26 cm-' and the CH2 out-of-plane wag at 965 & 23 cm-'.275 Ah initio calculations of vibrational wavenumbers for OC,OH+, where n = 3 - 8, suggest that their IR spectra would be dominated by a very few, very strong CC stretching bands.276Vibrational spectra have been reported and assigned (using ah initio calculations) for (6), where E = C, Si or Ge.277

DFT calculations of vibrational wavenumbers for Si2Cn.2,where n = 4 - 15, clusters suggest that for n = 4 - 13 linear structures are preferred, while for n = 14 or 15, cyclic arrangements dominate.278The IR spectrum of the linear molecule c g gave an assignment of the band centre of the a,,(antisymmetric) stretch to 2067.9779 cm-1.279 The high-resolution diode laser absorption spectrum of the CN radical gave band origins for v as follows: 2042.42104(84) cm-' for 12C14N,2000.08470(30) cm-' for 13C'4N.280 A detailed study of the IR spectrum of BrCN gave precise assignments to the 79Brand "Br isotopomers, e.g. vCN 2211.04292298 cm-' (79Br),2211.01046291cm-* (8'Br).281 The IR spectra of CO in Kr and Ar matrices gave assignments to the stretching fundamental of both monomer and dimer.282Bands due to v C 0 for CO.He, complexes, where n 20, were seen near 2145 cm-'.283 The IR spectrum of matrix-isolated CO.HON0 complexes gave evidence for the photochemical formation of trans- and cis-nitrosoformic acid, HOC(O)NO,

-

30

Spectroscopic Properties of Inorganic and Organometallic Compounds

with v C = O at 1858.5 cm-' (trans), 1822.3 cm-' (cis). Assignments were confirmed by isotopic shifts and ab initio calculations.284 Matrix-isolated IR spectra were reported for complexes formed by HNCS and CO. They were assigned using ab initio calculations for O C . . . HNCS.285A b initio and DFT calculations gave vibrational wavenumbers for carbon monoxide cyclic oligomers, (CO),, where n = 2 - 6.286 High-resolution FTIR spectra for 16012C170 and 16012C'80 in the range 15003000 cm-* gave assignments to many overtones and corn bin at ion^.^^^ An ab initio calculation has been performed to give vibrational wavenumbers for C 0 2 using second order perturbation theory.288 The overtone region of OCS was subjected to a high-resolution IR study, yielding values for v1+v3 (8954.87 cm-') and 5v3 (10080.91 ~ m - ' ) .High~~~ resolution IR data were reported and assigned for the clusters He,.OCS, where n = 2-8, e.g. for v,,OCS, 2062.4263 cm-' (n = 2), 2062.5676 cm-' (n = 8).290 Similar data were recorded for OCS.HZ, 0CS.HD and OCS.D2 complexes in liquid helium droplets (0.15 - 0.37K). Assignments for vasof the OC32Sforms are summarised in Table 7.291The same mode is centred at 2061.5053(2)cm-' in the complex CH4.0CS.292 A high-resolution study of the IR spectrum of DCOOD in the v3 (vC=O) region showed that the band centre was at 1725.1218(1)cm-'.293Table 8 summarises assignments of vibrational wavenumbers from the gas-phase IR spectrum of the F C 0 2 radical (assignments based on ab initio calculation^).^^^ DFT calculations on the carbonate radical anion C03'- show that the Raman spectrum can be accounted for by a structure with CZvsymmetry.295 A b initio calculations of vibrational wavenumbers were reported for the squarate ion C 4 0 t - and its compounds with Li+, Na+ and K+.296Resonance Raman excitation profiles have been reported for dithiosquarate, (7).297 Some re-assignments of overtone and combination bands of the trans and cis isomers of FC(O)OF, have been made on the basis of anharmonic vibrational calculations.298IR data have been reported and assigned for fluoroformic acid anhydride, FC(O)OC(O)F- Table 9.299Some TR assignments have been made for

Table 7 P-H2 o-H~ o-D~ P-D2 HD

Table 8 at

b, b2

Vibrational assignments for OC3*S.H2(lcm-') 2061.3659( 1) 206 1.495 9(2) 206 1.4226(2) 2061.552(3) 2061.39209(30)

Vibrational assignments for FCOz(/cm-*) %CO2 YCF 6CO2 Y co2 yasco2

PC02

1475 960 519 735 1098 474

31

2: Characteristic Vibrations of Compounds of Main Group Elements

1 2-

Table 9 v,c = 0 Y,,C = 0 v,C-F v,,c-0-c v,,C-F v,c-0-c 6FC(0)0 6,,FCO

Vibrational assignments for FC(O)OC(O)F (/cm-') 1941 1870 1249 1168 1030 938 765 652

[(F3C),B-C(O)F]-, including YC= 0 1829 cm-', YC-F1077 cm-' and 6COF 667 cm - 1 300 IR spectra and ab initio and DFT calculations gave a vibrational assignment for ClC(O)SX,where X = C1 or CH3.The vapours were shown to be 99% syn rotamer. Assignments included YC= 0 at 1775 cm-' (X = CH3)or 1801 cm-' (Cl).301 IR and Raman spectra of CH2ClC(O)NCOwere assigned using calculated wavenumbers from gauche and cis conformers from DFT and ab initio methods.302 Matrix IR data were reported and assigned for FC(0)SNCO (syn, syn conA b initio M.O. calculations gave former) and XC(O)SCF3,where X = C1 or Br.303 predicted vibrational wavenumbers for Cl-.[CF3C(0)CF3].304 The IR spectrum of CF3C(0)SOC(O)CF3included YC= 0 bands at 1838 and 1761 cm-'. The data were consistent with a syn, syn structure, and possibly < 5% of the anti, syn form.3o5 A high-resolution IR study of CH3CFZCl (including C1 isotopic data) gave . ~ ~ ~ - ~ Raman precise values for the band origins of v7 and Y ~ ~ High-pressure spectroscopy of CF4gave evidence for phase transitions at 8.9 GPa (phase I11 IV) and 13.6 GPa (IV -+V).308

-

-+

Silicon. - A b initio M.O. calculations gave vibrational wavenumbers for the anionic species HSi.Si-.309IR evidence has been found for the formation of dsilene, H2Si= SiH2,as one product of the Si + SiH4reaction in an argon matrix, with vasSiH2at 2207.8 cm-' (a,) and 2180.2 cm-' (bu),and 8SiH2(scissors)at 904.3 cm-' (bu).For (8), v,&H bands were seen at 1355.4 and 999.9 ~ m - ' . ~ ~ ' The Raman spectrum of Mes2Si=SiMes2, where Mes = mesityl, includes bands near 500 and 700 cm-l, due to in- and out-of-phase combinations of vSi = Si and Y , S ~ C ~Ab . ~ initio ' ~ calculations gave predicted vibrational wave4.2

32

Spectroscopic Properties of Inorganic and Organometallic Compounds H

numbers for Sin,where n = 7 - 11.312 The Raman spectrum of LiSi gave a band at 508 cm-', assigned as vSiSi from a SiSi3unit. A band at 622 cm-' was assigned as vSiSi from the three-coordinate silicide frarnew~rk.~'~ Raman spectroscopy was used to characterise silicon nanowires prepared by laser ablation at high temperature^.^'^ Raman spectra of nanocrystalline silicon films were used to monitor changes in vibrations with heating.315 IR and Raman spectra were reported for a-Si:H films prepared by hot-wire CVD. vSiH bands were seen at 2000 and 2090 ~ m - ' . ~FTIR ' ~ data (vSiH) were used to monitor changes in Si:H thin films (formed by CVD from SiH4/Ar mixtures) with changing SiH4 proportion^.^'^ The distribution of SiH, (x = 1 - 3) sites on the surface of plasma-deposited hydrogenated amorphous silicon (a-Si:H) films was established from IR data.318 ATR-FTIR studies on Si(100) surfaces in aqueous KOH media were used to follow changes in vSiH with solution concentration and electrode FTIR spectra of oxide-free silicon nanowires after etching with aqueous H F gave evidence for SiH, SiH2and SiH3surface groups.32oCalculations on hydrogenated amorphous silicon nitride suggested that vSiH of SiH2 groups would be above 2160 cm-', with vNH of NH2near 3450 c 1 ~ 1 - l . ~ ~ ~ Ab initio and DFT calculations gave predicted vibrational wavenumbers for Detailed studies of the IR and H2C = CHSiH = N(X), where X = H or OH.322-3 Raman spectra of EtSiHX2,where X = Br or I, showed that both contained antiand gauche-conformers in fluid p h a s e ~ . ~ Similar ~ ~ - ~ experiments on CH2 = CHSiF2H showed that cis- and gauche-rotamers were present in fluid phases.326 IR spectroscopy was used to characterise matrix-isolated C12(H)SiOCH3(from the HSiC13 + CH30H reaction), e.g. vSiH 2264 cm-', vSi0 1113 cm-', v,,SiC12 573 cm-', v,SiC12 513 The vSiH mode in R2(H)Si-N(M)R',where M = Na, K, R = Me, R' = CM3,SiMe3.328 The high-resolution FTIR spectrum of SiH2F2gave the band origin of v4 at 322.849389(173)C M - ' . Detailed ~~~ IR and Raman studies have been reported for EtSiH2X, where X = Br or I, showing the presence of anti- and gauche- conformers in fluid phases.330-'Similar studies on ClCH2SiH2X,where X = F, C1 or Br, show that the trans-conformers are the more stable in each A high-resolution study of the IR spectrum of CH3SiD3gave a value for v12of 583.94033(59) cm-' (high barrier model) or 593.94102(59) cm-' (free rotor A detailed assignments has been proposed for the IR and Raman spectra of CH3-,ClnSiH3,where n = 0 - 3, based on DFT calculations.335 IR (gas, solid) and Raman (liquid) spectra have been obtained for CH3CHClSiH3.The full assignments (confirmed by ab initio calculations) included a value of 152 cm-' for the SiH3 torsion.336IR and Raman spectra of

2: Characteristic Vibrations of Compounds of Main Group Elements

33

CH3CH2CH2SiH3and the Si-d3 isotopomer show that both anti- and gaucheconformers are present in fluid phases, but only the anti-form in the solid.337 High-resolution studies have been reported in the SiH overtone regions of H3SiD and HSiD3.338-9 Ab initio calculations have been carried out to obtain vibrational wavenumbers for intermediates in reactions in the SiH4/H2system, e.g. isomers of Si2H4 and Si2H2.340 Similar calculations gave vibrational wavenumbers for the clusters Si5H3,Si5H6, Si51i3and Si5Na3.All structures were based on trigonal bipyramidal Sis (D3h).341 Raman and FTIR spectra of epitaxial Sil,C, films include a band at 607 cm-' due to substitutional carbon atoms.342IR spectroscopy was used to follow crystallisation processes for amorphous S i c alloys in the temperature range 750 l100°C?43 IR and Raman spectra were used for characterisation of Sic nanowires formed on silicon substrate^.^^ IR data for silicon-rich a-SiC:H films deposited by d.c. sputtering include a band at 720 cm-' due to vC-Si of an H-Si-C group, with a feature at 780 cm-' also ascribed to Y C - S ~Ab . ~initio ~~ calculations of vibrational wavenumbers have been reported for isomers of Si2CN.346-7 Vibrational wavenumbers were also calculated by ab initio methods for S ~ ( C E C H )Detailed ~ . ~ ~ ~vibrational assignments have been reported from IR and Raman spectra of CHC12SiMe2H;349CH3CH2CH2SiF3;350 CH2=CHSi(CH3),C13-,, n = 1 or 2;3513,3-dimethyl-l-(trimethylsilyl)cyclopropene,352and 3,3dimethyl- 1,2-bis(trimethylsilyl)cyclopropene?53 The vSi-N mode due to an SIN, film formed by reactive pulsed laser ablation of silicon in a nitrogen atmosphere has been monitored by FTIR spectroscopy.354 IR and Raman spectra of plasma-enhanced CVD-deposited silicon nitride thin films have been reported.355Calculated Raman and IR wavenumbers have been obtained for cubic Si3N4.356 Raman spectroscopy was used to characterise silicon-rich SiO,N, thin films produced by plasma-enhanced CVD from N20/SiH4 mixt ~ r e s . ~ ~ ' An ab initio calculation of vibrational wavenumbers for Si(NC0)4enabled assignments of observed IR and Raman bands to be made in terms of Td symmetry.358 IR and Raman spectra have been reported for Si(N3)$- for the first time. The data are consistent with s6 molecular symmetry, and detailed skeletal mode assignments were given.359The IR spectra of (9,where R = Me, iPr, R' = H; R = R' = Me, all include vSiN bands near 900 ~ m - ' . ~ ~ ' IR spectroscopy was used to follow the oxidation of clean Si(100)-(2x 1) by molecular oxygen. There was evidence for the formation of a metastable silanone intermediate, (O)Si=O, with vSi=O at 1222 cm-' ( 1 6 0 2 ) , 1183 cm-' ('*OZ).~~' Several reports have been published of IR studies on a-Si0,:H film^.^^^-^ DFT calculations have given vibrational wavenumbers for model 3- and 4-membered rings in polymorphs of Si02.365 The Raman spectrum of Si02shows that high-pressure shearing (5 GPa) leads to formation of an amorphous state.366 IR and Raman spectra of S O 2 containing sodium aluminate show that the AI-0-A1 band weakens, and is replaced by an Al-0-Si mode on increasing Si02 c ~ n c e n t r a t i o n .Experimental ~~~ and theoretical vibrational studies have been

34

Spectroscopic Properties of Inorganic and Organometallic Compounds

R'

carried out on vitreous silica samples to probe both structural aspects and vibrational dynamics in such DFT calculations on (Si02),, where n = 4 - 14, show that rings are more stable than chains for n > 1l.372 The phase behaviour of hydrous y-Mg2Si04was followed by Raman spectroscopy (vSi0 region) at pressures of up to 56.5 GPa at room temperature.373 Thermally-induced phase transformations of y-Ca2Si04 (to 1723 K) were followed by Raman spectroscopy. There was evidence for the formation of an a< phase in the region 1073 - 1123 K.374High-pressure Raman spectra of the mineral ringwoodite (SO4stretching modes) were used to follow phase transitions (to approx. 40 GPa).375 Raman bands (vSi0) were used to study the structures of P-irradiated glasses in the Ca0-A1203-Si02system.376IR and Raman spectra in the CaO-La203Si02-P205phase system gave assignments to Si04and PO4 vibrational modes.377 The IR spectrum of Ce6[Si4013][SiO& includes a characteristic band at 648 cm-' due to a Si-0-Si bridge mode of the [Si4013] FTIR spectroscopy (vSi0) was used to characterise in situ fluorine-modified organosilicate glass thin films.379 The F T Raman spectrum of poly(dimethylsi1oxane) provided evidence for structure/spectra correlations with average chain length and the ratio of the number of monofunctional to quadrifunctional The Raman spectrum of poly(pentamethylcyc1o-pentasiloxane)was used to characterise the species, e.g. the final product contained a negligible number of SiOH The IR spectra of Cy7Si8012NH2, where Cy = C-CsH11, and related compounds all have vSiOSi as strong bands in the range 1100- 1120cm-', together with vNH 3400 3450 cm- 1.382 There have been several studies of the IR and Raman spectra of the SiF2anion as solid salts with a number of substituted ammonium cation^.^^'^ 4.3 Germanium. - The Raman spectrum of the cluster compound Na12Ge17 includes bands due to Ge2- and Ge2- units, i.e. the species can be represented as Na12{[Ge4]2Ge9).389The high-pressure Raman spectra of self-organised Ge/Si quantum dots gave data on the pressure dependence of Ge-Ge and Ge-Si modes.390Similar results were also obtained for germanium crystals embedded in a Si02matrix on a quartz-glass substrate.391

2: Characteristic Vibrations of Compounds of Main Group Elements

Table 10 YI y2 y3 y4

Table 11

v,GeO, K.isGe04 6asGe04 8,Ge04

35

High-resolution vibrational assignments for 70GeD4(lcm-') 15 10.51692(63) 660.82647(23) 1523.41352(12) 594.92632(13)

Vibrational assignments for YbGe04 (lcm-') IR

Raman

806 744,700 575,536 505

797 759,737,711,696 563 514

A high-resolution FTIR study of H70GeD3gave the following band centres: v1 2114.1477(46)cm-'; 2v14152.6817(14)cm-'; 5v19874.605(4)c111-l.~~~ High-resolution IR and Raman spectra of monoisotopic 70GeD4produced the data summarised in Table Laser-ablated germanium atoms and N2 in an N2 matrix react to give GeNNGe, whose IR bands are consistent with a linear structure. Numerous features were seen due to antisymmetric GeN stretching for isotopic variants, e.g. 70Ge14N'4N70Ge 891.83 Ab initio calculations have been reported for vibrational wavenumbers of linear germacyanogen isomers, e.g. GeNCN.395 Similar calculations have been performed on Ge(NC0)4.396 IR and Raman data have been reported and discussed for LnBiGe05, where Ln = Dy - Lu, Y. Assignments for Ln = Yb are summarised in Table ll.397 Vibrational measurements for KBGe2O6include vasof the G e 0 4 unit at 877 and 827 cm-', and vs at 552 and 587 cm-' cm-'.398 IR spectra for the glasses xMnO.(100-x)[Bi203.Ge02],where 0 5 x 4 50, include characteristic bands for the Ge04, Bi03 and Bi06 fragments.399The formation of germanium nanoclusters in bulk and thin-film germanosilicate glasses was observed from Raman scattering.4OO IR and Raman spectra gave vibrational assignments for the thiogermanic acids H4Ge4Sloand H2Ge4S9.401 The Raman spectra of GeS2-P2S5glasses gave evidence for GeS4/2tetrahedra, S = Ps3/2and PS3/2 units.402The Raman spectra of thin films of A S , G ~ ~ ~where ~ , S ~x ~=, 0,10,20,30,40, similarly showed that GeS4/2, and AS&,*units were present, together with Ge-Ge, As-As and S-S bonds.403 Structural changes with composition in glassy Ge,Sel-, samples were followed by Raman ~ p e ~ t r ~Thermal ~ ~ ~ phase p y .transitions ~ ~ ~ were reported for GeSe2 films at temperatures up to approx. 510°C.405The IR spectra of SbxGe28-xSe72 glassy semiconductors include bands due to nGeSe from GeSe4 tetrahedra and vSbSe from SbSe3units.406 Tin. - High-resolution IR and Raman spectra of monoisotopic lf6SnH4 gave very detailed molecular parameters relating to the vt and v3 4.4

36

Spectroscopic Properties of Inorganic and Organometallic Compounds

The IR spectrum of Me2Sn(Me2Pymt)2,where Me2PymtH = 4.6-dimethylpyrimidine-2-thione, includes a single vSn-C band (551 cm-'), showing that the SnMe2 unit is trans.408For, Me2Sn(PLP-2H),where PLP = pyridoxal 5'-phosphate, however, two vSn-C IR bands are seen, showing that the SnC2 unit is n~n-linear.~~~ The Raman spectra of Sn02nanocrystals include a surface-related vibrational mode, dependent on the Sn02 crystallite size.41oMicro-Raman and IR spectra have been reported for Sn02nanobelts synthesised from Sn and S n 0 2powders. The Raman spectrum shows a very strong band at 632.9 cm-' (alg),while two features are seen in the IR, at 701.9 cm-' (a2,) and 634.5 cm-l (eU(l)).411 A further report on Sn02 nanobelts indicated the persistence in them of rutile-like feat u r e ~Raman . ~ ~ ~spectroscopy was used to characterise DLC/Sn02 ~ysterns.4'~ IR and Raman spectra of [SnAs2S9I2-included vSS at 478 cm-', vAsS in the range 310 - 400 cm-', and vSnS as several peaks below 300 ~ m - ' . IR ~ ' spectro~ scopy was used to characterise structurally (SnS2)x(SnSe2)l-x crystals, where x = 0, 0.1,0.2,0.3,0.4,0.5,0.54,0.63,0.87,0.9 or 4.5 Lead. - Laser-ablated lead atoms react with H2 to give the following products trapped in an H2 matrix and identified by their IR features: PbH4 (vPbH 1815 cm-l, vPbD 1302 cm-'); Pb2H2(978.2,789.4 cm-', shifting to 737.5, 575.9 cm-' on deuteriation); Pb2H4 (1459.2, 959.4 cm-'; 1045.8, 702.6 cm-' for D); PbH3- (1383 cm-'; 995 cm-' for D). The data for the dinuclear species are consistent with dibridged structures."'6 The Raman spectra of (PbO),(P20s)l-, glasses, where x = 0.5 - 0.68, show a feature in the range 80 - 100 cm-' ascribed to vPbO. Quite detailed assignments were also made to PO:-, PO3-, P02- and P2074- modes!" Raman data for (60-x)Na20.xPb0.40P20s,where 10 s x s 50, gave evidence for the formation of Pb-0-P linkages at higher x values!18 The Raman spectra of Pb5SJ6 whiskers and tubules include vibrational modes characteristic of PbS and Pb12.419

5

Group15

5.1 Nitrogen. - Raman and IR spectra gave evidence for the formation of new phases of N2 at high temperatures and pressures (rp- and L-phases).420 Ab initio and DFT calculations have been carried out to give vibrational wavenumbers for the weakly-bound clusters (N2),,,where n = 3 - 6,421High pressure Raman spectroscopy gave evidence on structural phase transitions for nitrogen hydrate at pressures of up to 6GPa.422 DFT and ab initio calculations gave vibrational wavenumbers for N2H+.X, where X = He, Ne, Ar, Kr, Xe or H2.423The first report has been made of a very weak IR band due to vN-N of hydrazine. The band origin was at 1077.24056(82) cm-l .424 Detailed vibrational assignments have been given for N2H4and N2D4based on ab initio ~ a l ~ ~ l a t i o n ~ ~ ~ ~ The Raman spectrum of N 2 0subjected to high temperature and pressure and

2: Characteristic Vibrations of Compounds of Main Group Elements

37

then quenched included features due to NO+N03-.426A high-resolution study has been reported for the v1+v3 band of N 2 0 (3447.678 ~ m - ' ) The . ~ ~high~ resolution FTIR of the (N20)2dimer shows that the band origin of v3 of the N20 unit is at 2247.83 cm-' - due to coupling with the dimer torsional mode.428 A high resolution study of vasN20gave the following band centres: N20.3He 2223.9737(1) cm-', N20.4He2224.0099(1) ~ r n - ' .Similar ~ ~ ~ measurements were carried out for the complexes N20.H20and N20.D20.430 A b initio and DFT calculations of vibrational wavenumbers have been performed on the halocarbonyl azides, C(X)O-NNN, where X = F, C1 or Br.431IR and Raman spectra gave vibrational assignments for the ion [N(N02)2]-, as the [Ag(~y)~]salt - Table 12.432DFT calculations gave predicted vibrational wavenumbersfor N(NH2)32+ and N(N3)32+ .433 Vibrational assignments have been proposed, from IR and Raman data, for N5+,as the SnF62- salt - Table 13.434 The FTIR spectrum of matrix-isolated HNC0.H20 (in argon, 20K) gave assignments to HNCO modes, backed up by ab initio calculations. YNH of the HNCO unit is at 3296 cm-', compared to 3511 cm-' in free HNC0.435The IR spectrum of HNCS.N2 in a xenon matrix includes YNH at 3492.6 cm-', compared to 3508.5 cm-' in the monomer."36 The dimeric species [RA1(p-NHEt)(p-NEt)2Si(NHEt)]2,where R = Me or Et show terminal vNH at about 3410 cm-', bridging vNH near 3260 Photoinduced reactions between NH3 and F2 in solid argon gave a range of species identified by IR spectroscopy. Assignments for FH2N-HF, H2N'-HF. . . F' and NH-HF-HF are summarised in Table 14.438IR and Raman spectra have been reported and assigned for carbamoyl azide, H2NC(0)N3,using C, sym+

Table 12

Vibrational assignments for [ N ( N 0 2 )

v,,N02 in-phase v,N02 in-phase vsN3 6scissN02 in-phase v,,N02 out-of-phase vSNO2out-of-phase Va33

GrockN02 out-of-phase

Table 13

21-

IR

Raman

1593,1527 1341 952 825 1440 1176 1066,1018 728

1570 1329 943 828

(lcm-')

1226,1153 1073,1039

Vibrational assignments for N S (Czusymmetry) (lcm-') +

2287 2227 1112 88 1 672 475 417 417 203

38

Table 14

Spectroscopic Properties of Inorganic and Organometallic Compounds

Observed infrared bands for photolysis products of A Y / F ~ / ' ~ N H ~ .

(lcm-9 FH2N-HF

HzN.-HF. . . F.

NH-HF-HF

722 750 933 1243 1314 1568

7991806 1468 1514 3180/3206

5 131515 597 699 947 3450 3721 3268 3387

metry. The assignments were supported by a normal coordinate analysis.439 The NH3+.Ar complex gave the following assignments: v1 (al) 3117.4 1 cm-', v3(al) 3336 & 1 cm-', v3(b2)3396.26 0.13 cm-'. The combination of v1 with the intermolecular stretch is seen at 3305.5 f 2 cm-1.440A b initio and DFT calculations gave predicted vibrational wavenumbers for NH3+.Arn,where n = 0 - 5.441 Similar calculations gave vibrational wavenumbers for NH3(H20), clusters, where n = 3 or 4,442and for hydroxylammonium nitrate, HONH3+N03-.443 IR and Raman spectra gave detailed vibrational assignments for (CH3)4E+, where E = N, P, As or Sb. The assignments were based on the results of ab initio calculations, and included v,C4E (al):753 cm-' (N), 648 cm-' (P),591 cm-' (As), 536 cm-I (Sb).444 The high-resolution FTIR spectrum of 1,2,4-triazine, C3N3H3, gave the following band centres: v20(a") 367.88 cm-l; vZ1(a") 311.28 cm-1.445

A b initio calculations gave vibrational wavenumbers for NO2+in a number of electronic states.446DFT calculations for the N O dimer radical, suggest The IR the assignment of an IR band at 1424 cm-' to the cyclic structure spectrum of N O adsorbed inside SWCNT shows that it is present exclusively as cis-(NO)2,withv1 1853 cm-' (symm.), v5 1754 cm-' (anti~yrnm.)!~~ Intracavity laser absorption spectra have been analysed for NO2,showing that o1is near 1265 cm-' (vJ, w2 near 738 cm-' (6) and ( u 3 (vaJnear 775 cm-'.449An ab initio calculation of the vibrational spectrum of HONO gave reasonably good agreement with e~periment.4~' The FTIR spectra of complexes of cis- and transHONO with NO2in argon matrices show that the O H group of HONO acts as a proton donor to the 0 of N02.45' The IR spectrum of CF3CH(ONO)CF3includes YN= 0 at 1766cm-I, vCF3at 1302, 1210 and 1119 cm-', and 6 0 N O at 761 FTIR data have been

2: Characteristic Vibrations of Compounds of Main Group Elements

39

Table 15 High-resolution vibrational assignmentsfor HN03. (/em-'). 647.826262 580.303505 763.154270 458.228664

reported for ClN02 in the solid state and in frozen water in the temperature range 10 - 200K. No thermally induced reactions with H 2 0 were detected.453 DFT calculations have given sets of vibrational wavenumbers for nitryl chloride, cis- and trans-chlorine nitrite.454The high-resolution FTIR spectrum of 81BrN02 gave the band centre of v2 as 787.143175(27)cm-' (787.156375(26)cm-' for the 79Brform)."55 Ab initio calculations gave predicted vibrational wavenumbers for the radical N03'-.456 Table 15 summarises the results of high-resolution studies on HN03.457 RAIR spectra of solid nitric acid hydrates gave assignments based on a b initio cal~ulations.4~~ Predicted vibrational wavenumbers for CO.HON02 and OC.HON02 were obtained by means of ab initio calculation^."^^ Similar calculations were also reported for N2.HON02t6'and 02N.HON02.461 The high-resolution FTIR spectrum of 35C10N02gave the band origin for Yg at 711.20763(9) cm-', while that for v9 was calculated to be at 123.7219(20) cm- 1.462 The high-pressure Raman spectrum of NOfN03- to 40 GPa at room temperature, and to 14 GPa down to 80 K, was used to probe structural

transformation^.^^^ IR and Raman spectra gave vibrational assignments for triphenylmethyl N-sulfinylamine (trityl-NSO) - the first alkyl N-sulfinylamine to be fully structurally chara~terised.4~~ Quite detailed IR and Raman assignments were proposed for (11)and the analogous d i ~ a f i o n . 4 ~ ~

(1 1)

High-resolution FTIR data for 14NF3were analysed to give the following band origins: v2 647.1340617(73)cm-', and v3 907.541330(7)cm-1.466-7

Phosphorus. - Ab initio calculations of vibrational wavenumbers for P2R4, where R = Me, SiH3, gave values generally in good agreement with experiment.468GaP doped with silicon gave IR bands at 2175.1 and 2190.3 cm-', assigned as YPH modes.469IR and Raman data have been reported for HP(C6F5)2, including YPH 2370 cm-' and YPC 844,823 ~ m - ' . ~ ~ ' IR and Raman spectra gave detailed vibrational assignments for CH3PF3H (and the dl-analogue), Table 16; 471 and for [CH3PF4H]-, Table 17.472 5.2

40

Spectroscopic Properties of Inorganic and Organometallic Compounds

Table 16 Some vibrational assignmentsfor CH3PF3H(/cm-'). vPH/D VPC vPF(eq) vPF2(ax)

2564/1856 7 12(H)/620(D) 828(H)/771(D) 798(H)/?771(D)

575(H)/573(D)

Table 17

Some vibrational assignmentsfor [CHjPFdHI- (/cm-*).

vPH VPC vasPF2 v,PF4(in-phase) GPF,(umbrella) vsPF4(out-of-phase)

2343 752 683 563

538 484

High-resolution studies have been carried out for PH3in the regions of ~ ~ / ~ 3 4 ~ and ~ 2 / ~ 4Other, ? ~ ~ related, high-resolution studies involved PH2D, PHD2 and Ab initio calculations gave values of vibrational wavenumbers for PD3.475-481 (PH3)2.482 IR spectra revealed differences between the all-cis- and cis-trans-isomers of [(Ph)(Me)PNJ, e.g. in the all-cis form YP=N bands are seen at 1186,1170 cm-l, and in the cis-trans form at 1183, 1167 c11l-l.~~~ Ab initio calculations gave predicted vibrational wavenumbers for (PNX2),, where X = H, F, C1 or Br; n = 2 - 6.484DFT calculations gave vibrational wavenumbers for polymorphs of P3N5.485 Raman and IR spectra have been reported and assigned for Pb(03PC&). There was evidence for strong hydrogen-bonding between the lone pairs of the CP03 unit and the phenyl hydrogen atoms.486Raman spectroscopy was used to follow structural changes in ( l - ~ ) N a P 0 ~ . x A l ( P glasses 0 ~ ) ~ with changing x. vSP02showed significant changes for x > 0.17.487 Variable-temperature Raman spectra gave evidence for temperature induced phase transitions in Li3P04.488 IR and Raman spectra at high temperatures were used to track phase transitions in the Na3P04-GaP04system. There was evidence for non-equivalence of PO4tetrahedra and their statistical distribution in the glass-forming regi0n.4'~Assignments were made to YPO and 6PO modes from the IR and Raman spectra of solid solutions, Ba3.xSrx(P04)2, where 0 s x s 3:90 The Raman spectra of M3(P04)2.8H20,where M = Mg or Fe, minerals contained YPO bands showing great similarity between them?91The IR and Raman spectra of the new polyphosphate KBi(P03)4contained characteristic bands of infinite chains of PO4 tetrahedra linked by a bridging oxygen atom.492 Raman assignments for (1-x)Na20.xP205,where x = 0.25,0.33,0.5 or 1, have been given. YPOmode assignments were based on ab initio calculations, in terms of the number of bridging oxygen atoms connected to each phosphor~s.4~~ The Raman spectrum of (PbO)o.5(P205)o.5 doped with Tho2 was consistent with the presence of PO4units having two non-bridging oxygen at0ms.4~~ IR and Raman

2: Characteristic Vibrations of Compounds of Main Group Elements

Table 18

41

Some Vibrational assignmentsfor [CH3PFJ- lcm-I).

YasPF2

vPF4(in-phase) vPF(ax) GPF4(umbrella) vPF,(out-of- phase)

(a’) (a’) (a’) (a’) (a’)

752 683 550 518

498

spectra of MM’4(P309)2species, where M = Ni, M’ = Na, Ag; M = Cu, M’ = K; M = Zn, M’ = Rb, were all assigned in terms of P309modes. All except the last (C,) were consistent with D3h The Raman spectrum of rhombohedra1 P4Ol0yielded detailed vibrational assignments. Effective C3” symmetry was found, and five new e modes were reported (262, 329, 419, 829 and 846 cm-1.499The Raman spectrum of a new ozonide of P406,i.e. P4018, included bands at 901, 887 and 870 cm-’ due to modes of the PO3ring ~ n i t s . ’ ~ Vibrational assignments have been proposed for [CH3PF5]-. Some of these are listed in Table 18?01The IR and Raman spectra of PX4+,P2X5+ and P&+, where X = Br or T, were backed up by ab initio ca1culations.so2The compound ( N a p ) ( p B ~ ~(12), ) ~ , has vPBr at 378 and 351 cm-’. For (NapP2),, vPP is at 416 cm- 1 503

Arsenic. - The compounds R3As[ON = C(Me)Ar12,where R = ‘Pr or iBu, Ar = C5H4N-2or C4H30-2,all show vAsC in the range 580 - 670 cm-’, vAsO 427 - 435 cm-’ in their IR Skeletal mode assignments have been proposed from the IR and Raman spectra of A~Cl(N3)~(py) and SbC12(N3)(py)2 Table 19.505 The Raman spectrum of arsenolite, As406, has been fully assigned for the first time. The previously unseen egmode is at 443 cm-1.506 IR and Raman spectra gave assignments to vAs-S(t) and vS(b)-As-S(b)modes in orpiment (As2S3),smithite (AgAsS2)and lorandite (TlAsS2),and also to analogous Sb modes in stibnite (Sb2S3),miargyrite (AgSbS2)and weissbergite(T1SbS2).’07 The Raman spectrum of realgar (As4S4)includes vAsS bands at 374,367,353,340 and 327 cm-’, GAsS bands at 219,210,191 and 181 cm-’. For orpiment (As2&), vAsS bands are at 382,355,325,310 and 294 cm-’, GAsS bands at 202 and 180 Ab initio and DFT calculations gave vibrational wavenumbers for As4S4 of D2dsymmetry.509The Raman spectra of A s ~ S ~ Swhere ~ ~ - x~ ,= 0 - 3, gave assignments to antisymmetric As-(S,Se)-Asstretches at 340 and 230 c ~ - ’ . ~ ’ O

5.3

Spectroscopic Properties of Inorganic and Organometallic Compounds

42

Table 19

Vibrational assignments for arsenic and antimony azide complexes. (/em- ').

v,MN(azide) v,,MN(azide) 6 MN(azide) v,MCl v,,MC1 YMNPY) GMNPY)

Table 20 SbH3 all SbH2 (v3, b2) SbH 9-2

(Vl,

Table 21 BiH3 BiHz (v1, ad BiH2 b3, b2) BiH

452 432 265 287 216 139

386 24 1 326 285 157 108

Vibrational assignments for SbH, in a neon matrix. (/cm-'). 1894.4 (H)/1360.8 (D) 1883.9 (H)/1352.0 (D) 1879.0 (H)/1349.4 (D) 1858.2 (H)/1331.8 (D)

Vibrational assignments for BiH, in a neon matrix. (1cm-I). 1733.6(H)/1243.4 (D) 1698.0(H)/1218.5 (D) 1704.9(H)/1223.0 (D) 1635.9(H)/1171.9 (D)

The Raman spectrum of N2H6(AsF4)Fcontains characteristic bands for A S F ~ - . Raman ~'~ data for M+As4FI3-,where M = Rb or Cs, show that they are give VEXbands at 350 cm-' (E = As, iso~tructural.~'~ IR spectra of (C4H3S)3EX2 X = Cl), 289 cm-' (E = Sb, X = Br).513

Antimony and Bismuth. - Laser-ablated E atoms ( = Sb or Bi) react with H2 to form EH, species, where n = 1 - 3. Vibrational assignments from their matrix-IR spectra are given in Tables 20 (E = Sb) and 21 (Bi).514A highresolution IR study of SbH3gave results shown in Table 22.515 The far-TR spectra of M[CS(NH2)2]313, where M = Sb or Bi, show that the thiourea is N-bonded to M.516IR bands are seen in the range 410 - 460 cm-' for Ph3Sb[ON = C(CH3)ArI2,where Ar = C5H4N-1,C4H3S-2,C4H30-2etc517IR and Raman spectra for (13) gave skeletal assignments, e.g. v,,SbOSb 675 cm-', v,,SbOO(H) 520 cm-' and vSbO(br) 464, 445 c111-l.~'~ The Raman spectra of glasses xSb203.(1-x)ZvC12,where x = 0.25,0.50,0.75or 1.0, gave evidence for the species Sb(OSb)2(OZn).519 The Raman spectrum of (AgI)*Ag3SbS3 is dominated by SbS3*- bands at 357, 327 and 316 ~ m - ' . ~The ~ ' Raman spectra of thin films of Sb2S3dopedwith Sm3+ Ab initio calculations ions give bands due to SbS3 pyramids and S-S confirm the formation of Sb2S52-and Sb2S2- by the oxidation of Sb by elemental sulfur and p o l y ~ u l f i d e s . ~ ~ ~ 5.4

2: Characteristic Vibrations of Compounds of Main Group Elements

Table 22

Y1 v2 v3

v4

43

High-resolution vibrational assignmentsfor SbH3. (/crn-').

1890.502818(106) 1890.400645(109) 782.245129886(79469) 782.134434412(74208) 1894.4972453(588) 1894.3751455(669) 827.854502621(68014) 827.825104638(63049)

H

(13)

DFT calculations gave predicted vibrational wavenumbers for Sb2FI (D4h symmetry) and for pyrazine.2SbF5(D2h).523 Raman spectroscopy was used to characterise bismuth nanoparticles prepared by laser ablation techniques. The wavenumber and bandwidth of the algmode showed little change with particle size.524High-level computational methods were used to verify experimental vibrational assignments for BiH3.525 The compound (4-BrC6H4)3Bi(02CCH2CH2GePh3), and related species, show vBiC bands in their IR spectra in the range 450 - 480 c 1 ~ 1 - l . ~ ~ ~ SERS data on the mechanism of electroreduction of peroxide on a bismuthsubmonolayer modified Au(111) surface gave evidence for the formation of Bi-OH and Bi-0 species, e.g. G,Bi(OH)2near 970 cm-'.527 The IR spectra of xMn0.(100-x)Bi203samples contain bands due to Bi03 and BiO6 u n i t ~ . ~The " Raman spectrum of Bi12Mx020+dshows bands below 650 cm-' due to vBiO motions.529 IR and Raman spectra of BiSCl crystals show vBiS features near 600 cm-', with vBiCl below 200 c ~ - ' . ~ ~ O - ' Variable temperature Raman spectroscopy was used to probe phase transitions of ( ~ y H ) ~ B i ~atc122 l ' ~ and 154 K.532

6

Group16

Oxygen. - Calculations have been carried out on 02-.(H20),,, where n = 1 The new zeolite-like species Ca12Al10Si4035 gave Raman bands showing the existence of 02-and 02- in the cavities of the framework.534The resonance Raman spectrum of 02- in Cs202 gavev at 742.5 cm-', 2v at 1468.5cm-' and 3v at 2176.8 cm-'. These showed that 0.3 cm-'.535 me was 759.5 _+ 0.7 cm-', and O e X e 8.4 Tunable diode laser spectra of the H 0 2 radical showed that the 0 - H stretch overtone was centred at 6651.1876138 cm-'.536Vibrational assignments have 6.1

- 4, to help explain the IR spectra of these

44

Spectroscopic Properties of Inorganic and Organometallic Compounds

been proposed for the radical complex HOO-S02.537 IR data have been reported for the trifuoromethoxycarbonyl peroxy radical, CF30C(0)O0,in noble gas matrices, e.g. vC = 0 1903 cm-' (trans,trans, trans), 1875 cm- (trans, trans, cis).53sFor perfluoromethyl fluorocarbonyl peroxide, CF300C(0)F, matrix IR data show the presence of both syn- and antir0tame1-s.~~~ IR and Raman data were reported and assigned for CF,OC(O)OOC(O)F, trifluoromethyl fluoroformyl peroxycarbonate, including v C = O bands at 1913 cm-'(IR)/1906 cm-'(Raman) and 1875 cm-' (IR)/1866 cm-' (Raman) and Y O - 0at 924 cm-' (IR and Raman).540 showed 60 that the band centre for v3was at High-resolution FTIR for 1601g01 1008.452762 ~ m - ' . ~High-resolution ~' FTIR data were also reported and anaisotopomers of 03.542 A b initio calculalysed for the 5v3 overtones of all 160/'80 tions have been carried out to give vibrational wavenumbers for the 1:l complex 03.H20.543 Intermolecular vibrations of the OH-CO complex were observed as combination bands in the OH overtone region.544H/D isotopic shifts were used to confirm vOH/vOD assignments for the H20.HO radical complex.545 DFT calculations gave predicted vibrational wavenumbers for this species.546 A b initio M.O. calculations were reported for the wavenumbers of 6HOH modes for (H20)n,where n = 6 - 10, cage Similar calculations for e-.(H20)n (n = 2 - 6) and e-(HOD), (n = 2 - 5) gave excellent agreement with vOH values observed e~perimentally.~~' Other reports of calculated vibrational wavenumbers by ab initio methods were given for Br-.(H20)n (n = 1 - 6);549 (H20)2..HX(X = H, F, C1, Br) and (H20)2..C1F;550 clusters of H 2 0 molecules and simulating liquid water;551the cluster H24O12 based on 4454cage (HF)n(H,O)m(n m 2 2).553 A detailed study of the IR spectrum of H2160 in the range 3367 - 3447 cm-' gave gas-collision -broadened line The emission spectrum of HDO at 1500°C gave the following band centres: v2 1403.48 cm-', v1 2723. 68 cm-', v3 3707.47 ~ r n - ' .High ~ ~ ~resolution studies have been reported for H 2 0 molecules A matrix-isolation study of the H20-HO radical in the OH overtone complex shows that vOH of H20 is at 3634.6 cm-' (2655.6 cm-' for the D-analog~e).~~~ The gas-phase IR spectrum of the H+(H20)2cluster gave assignments to modes of the 0 . .. H + . . . 0 unit, e.g. [O . . . H . . . 01, bend 921 cm-', [O . . . H . . . 01, bend 1043 cm-' and [O . . . H . . . 01 antisymmetric stretch 1317 ~ r n - ' . ~ ~ ~ Molecular dynamics calculations suggest that the band near 170 cm-' for liquid water can be assigned to the hydrogen-bonded network, but that the band near 60 cm-' cannot.560 Picosecond TR3 data for H 2 0 under resonance with the electronic transition of the solvated electron gave values for modes of H20 in direct contact with the e l e c t r ~ n .Semi-classical ~~' calculations were reported for the intramolecular vibrations of dilute HOD in liquid D20.562Raman data have been obtained to probe the effects of metal cations on water ~ t r u c t u r e . ~ ~ ~ - ~ Theoretical calculations have been made for the vOH wavenumbers for ice Ih.566Characteristic Raman bands were reported and discussed for ice IV.567

'

+

2: Characteristic Vibrations of Compounds of Main Group Elements

Table 23

32~32~160

32~34~160 34~34~160 32~32~180

45

Vibrational assignments for cyclic-SZO isotopomers in an argon matrix ( / c m - l ) . Y1

y2

y3

799.1 795.1 791.O 770.5

544.1 537.4 530.7 539.0

575.4 571.6 568.0 555.9

Raman spectroscopy was used to follow the phase behaviour of ice VIII at pressures greater than 10 GPa.568

6.2 Sulfur. - DFT and ab initio calculations have been made for the vibrational wavenumbers of FC(0)SSMe in the neutral ground state and in the lowest-lying cationic state.569Photolysis of disulfur oxide SSO in an argon matrix at 13 K produced cyclic-S20,with assignments summarised in Table 23.570 Variable temperature Raman data for liquid sulfur in the region of the polymerisation transition point gave evidence on the structural changes in this region.571Ab initio M.O. calculations gave predicted IR and Raman wavenumbers for Se,Ss_, molecules - in good agreement with available experimental data.572New IR and Raman data were used to establish structure-property relationships in As-S-Se glasses. S-S bands were seen in the region 440 - 480 cm-', Se-Se bands near 255 ~ m - ' . ' ~ ~ There is matrix-IR evidence for the formation of an (H2S)2dimer in krypton/H2S matrices (a strong band at 2575 ~ m - ' ) . ~ ~ ~ IR and Raman spectra of FC(0)NSC12, i.e. N-(fluoroformy1)imidosulfurous dichloride, gave detailed assignments, confirmed by ab initio calculations. YS = N was seen at 1245 cm-' (IR), 1233 cm-' (Raman), Y ~ S C ~ ~ 455 / ~ cm-' ~ ~ S C ~ ~ (Raman).575 A high-resolution FTIR study of v2 of SOF2 shows that it is centred near 808 cm-l .576 The FTIR and Raman spectra of Et,SO show that the YSO and vCH regions for solid, liquid and solution samples can be analysed in terms of 7 components.577 The compounds (14), where R = Me, 'Bu, Ph or p-MeC6H4, have IR bands due to YS = 0 in the range 1060 - 1065 c111-I.~~~

Reflection FTIR spectra were reported for SO2 and S02/H2O thin films between 10 and 200 K.579Ab initio calculations have been carried out of the

46

Spectroscopic Properties of Inorganic and Organometallic Compounds

vibrational wavenumbers for halosulfonyl a z i d e ~ . ~ ~ ' Several high-resolution studies of SO3 (FTIR and CARS) gave the following band origins: v1 1064.924(11)cm-',v2 488.799189(17)cm-' and v4527.681547(13) cm-l .581-3 The IR spectrum of SO2 in aqueous solutions gave evidence for HOS02- (from YOH), with some contributions from the HS03- isomer and H2S202- .584 Ab initio M.O. calculations gave vibrational wavenumbers for methanesulfonic acid - which were used to interpret experimental Raman Raman spectra of concentrated sulfuric acid mixtures were used to estimate hydrogen bond enthalpies between H30+ or H502+ and HS04-.586-7Raman spectroscopy was used to study the proton dissociation of HS04- in aqueous sulfuric acid solutions.588Raman spectra of aqueous H2S04 over ranges of temperature (220 - 300 K) and composition (12 - 81 wt% H2S04) were used to obtain ionic speciation, based on the relative intensities of the HS04- band at 1050 cm-' and the SO?- band at 980 c ~ l l - ' A . ~detailed ~~ study of the IR spectra of the H2S04/H20system gave unequivocal evidence for H2S04.(H20)8.590 Several studies have been made of the effects of site symmetries on v S 0 modes of SO?- incorporated in ionic lattice^.^^'-^ Variable-temperature IR and Raman spectra of CsHS04 gave evidence for phases I, I1 and 111, but could not confirm phase IV.594 DFT calculations gave vibrational wavenumbers for H2S04.CO, H2S04.0C and three H2S04.(C0)2complexes.595Similar calculations were performed on H2S04.(C02),,where x = 1 or 2.596The Raman spectrum of polycrystalline Cs~.26Rbo.74H(S04)o.89(Se04)~.~~ gave assignments to vA-OH and v A - 0 (A = S or Se) modes as a function of temperature.597Ab initio calculations gave vibrational wavenumbers for S2072- (C2 symmetry), which were compared to experimental values from molten M2S207, where M = K, Rb or C S . ~ ~ ' High-resolution FTIR studies on 32SF4gave the following band centres: v1 (v,SFeq)891.5679 cm-'; v6 (v,,SF,,) 729.6836 cm-'; vg (vasSFeq)864.5935 C I I I - ' . ~ ~ ~ 600

6.3 Selenium. - IR and Raman spectra have been reported for motions of a regular helical chain in amorphous selenium.6o1Ab initio calculations of vibrational modes were used to assign these experimental values.602 Characteristic vSeSe, vSeTe and vTeTe features were found in the Raman spectra of Se,Te,., thin films.603The Raman spectra of Ge,Sel-, glasses gave assignments to vSeSe (value dependent on the germanium concentration) and Y G ~ S ~The , ~Raman . ~ ~ spectra of samples in the Se-Ag-I system show that the introduction of Ag and I brings about a shift in the Se-Se chain stretching mode from 251 cm-' to about 236 cm-'. It was suggested that this was due to a trigonal type of chain formation.605 The high-pressure (to 23 GPa) Raman spectrum of Se02 showed that structural transformations occurred near 7 and 17 GPa.606The IR and Raman spectra of Mn3(H20)(Se03)3 and Mn4(H20)3(Se03)4 gave the expected values for Se032modes.607 6.4

Tellurium. - The IR and Raman spectra of Te2R2(R

=

CF3, C6F5)and

2: Characteristic Vibrations of Compounds of Main Group Elements

47

Te(C&'5)2 gave vibrational assignments, e.g. for R = C6F5, vTeTe 190 cm-', v,,TeC2 230 cm-', v,TeC2 279 cm-'. All Te2R2modes were consistent with C2 skelet a1 symmetry.608 Variable-temperature Raman spectra of T e 0 2crystals gave evidence for structural changes, with suggestions for the possible structure of the melt.609Structural changes in the TeO2-T1F and Tl2Te3O7-T1Fsystems were followed by Raman spectroscopy.610Raman data were reported for (Te02)1,(PbC12-,0,~2)y glasses (y = 0.13 - 0.64, z/2 = 0.45 - 0.64). These show that the proportion of T e 0 4 trigonal pyramids increases with increased modifier content.61' IR spectroscopy was used to characterise (uia nTeO modes) ( 1-x)Te02.xW03glasses, where 0 5 x 5 0.325.612 The F T Raman spectrum of [C13Te-F-TeC13] contained the bands expected from theoretical ~alcu latio n s.~ '~ +

7

Group17

Ab initio calculations of the vibrational wavenumbers of HF2-.(H20)2 suggested that a ring structure would be preferred.614 Matrix-isolation F T Raman spectra have been reported for CO.XY, where XY = Cl2, BrCl, or ICl. The following nXY assignments were proposed: C12 545.0 cm-' (35Clz), 537.6 cm-' (35C137C1), 530.3 cm-' (37C12); BrCl 428.4 cm-' (79BrC1), 427.0 cm-' (81BrCl);ICl 369.6 cm-' (13'Cl), 361.7 cm-' (I"7CQ6l5 Evidence was found for both C13- (v,C13 286 cm-') and C15- (466 cm-') from [PPh2C12] +Cl3-.Cl2in CHC13/C12solution.616 The intermolecular out-of-plane torsion in (HC1)2was probed using combination bands with intramolecular H-Cl stretching IR cavity ringdown spectroscopy of HCl.H20 gave at 2723.1 cm-* (1976.0 cm-' for the DCl HCl/H20 clusters were studied by IR spectroscopy in a supersonic jet. A firm assignment was made of nHCl in HCl.H20 (2723.5 cm-'), and a tentative assignment for HCl.(H20)2(2464 ~ m - * ) .Detailed ~'~ studies have been reported of vibrational parameters for HCl/DCl dissolved in SF6.620-1

A detailed matrix-isolation IR study has been reported for radicals ClO,, where x = 1- 4, in a neon matrix. For C10, we was at 526 cm-' (x2n3/2 state), 527 cm-' (X2111/2state). For C102,the data were consistent with the dimer (15), Table 24. Assignments for x = 3 and 4 are given in Tables 25, 26 respectively.622TR3 data were used to probe the photoisomerisation and geminate recombination

48

Table 24 YasC10* YSC1O2 6,C102 YC1202

Table 25

Spectroscopic Properties of Inorganic and Organometallic Compounds

Vibrational assignments for (ClO2,lz in a neon matrix (/crn-'). 1107,1096 93 1,927,925 464,451 175

Vibrational assignmentsfor C103in a neon matrix (Icm-').

(all data relate to the 35C11603 isotopomer)

Table 26 YO-0 vasC103 YsC103 vc1-0 6,,C103

Vibrational assignments for C104in a O2 matrix (/cm-'). 1525.4 1252.1/1229.4 1012.7 687.8 593.61573.5

(all data relate to the 35C1'604isotopomer)

processes for ClOO Fundamental modes of "C104-, where n = 35, 37, doped in a K M n 0 4 matrix can be assigned on the basis of effective C2" symmetry.624 The 'hydrogenic' stretching mode of BrHBr- (from the vibrational predissociation of BrHBr-.Ar) was assigned as 733 cm-'.625The FTIR spectra of (HBr), clusters, where n < 4, in supersonic jet expansions gave the first reported gas-phase data for n = 3 or 4.626 The stretching mode of the I2 molecule in Cr(Pc)12.12gave a resonance Raman band at 180 cm-', showing that there is only weak interaction with the axial atoms of C ~ ( P C ) I ~ . ~ ~ ~ The IR and Raman spectra of trans-[I02F5I2- gave the assignments shown in Table 27, which were confirmed by ab initio calculations.628IR and Raman

Table 27

Some vibrational assignmentsfor trans-[102F5l2- (Icrn-'). ~

~

~________

789 (Raman) 5 17 (Raman) 847 (IR) 330 (IR) 490 (IR) 390 (IR) 368 (Raman) 395 (Raman)

2: Characteristic Vibrations of Compounds of Main Group Elements

49

spectra also gave assignments to anion modes for Ca[H412010].4H20.~~~ The complex [NbPc2][IBr2] gave a Raman band at 172 cm-' due to the anion.630

Group18

8

IR data were reported for the complexes of HXF (X = Ar or Kr) and HKrCl with N2, e.g. for HArF..N2nH-Ar is at 2002.2/2029.7 cm-', while for HKrF..N* vH-Kr is at 1936.5 ~ m - ' . ~Ab~ initio ' calculations gave vibrational wavenumbers for the linear hydrogen-bonded complex OC..HArF, in which vH-Ar is shifted 10 cm-' to higher wavenumbers compared to free HArF.632 IR evidence has been found for the new krypton compound, HKrCCH, in a krypton matrix, with vCH 3290 cm-', vH-Kr 1241.5 cm-', GCC-H 610 An ab initio calculation of vibrational wavenumbers for N2..HKrFsuggested that there should be a high wavenumber shift of about 60 cm-' invH-Kr compared to free HKrF.634Experimental values were found for vKrF in [KrF][AuF6], with vKrF(t) 600.2 cm-', vKrF(br) 391.9 cm-'.635 Ab initio calculations have been made or the vibrational wavenumbers for the dimer (HXeH)2.636 IR data have been reported for the xenon-matrix-isolated species HXeCCH (vHXe 1486 cm-', vCH 3273 cm-'), HXeCC (vHXe 1478 cm-', vCC 1748 cm-I), HXeCCXeH (vHXe 1301 cm-') - the last is the first neutral molecule containing two rare gas A neutral xenon-containing radical, HXeO, has been reported, from the photolysis of H20/Xe matrices, with vHXe at 1466.1 cm-' (1070.3 cm-' for v D X ~ )The . ~ IR ~ ~spectra of xenon matrices containing HXeOH/H20 included bands at 1681 and 1742 cm-' due to HXeOH.H20, HXeOH.(H20)*respectiveiy.640 There is Raman evidence for the formation of an Xe-Si02 species at 0.7 - 1.5 GPa and 1500 - 1750°C.641IR and Raman data have been reported for Ba(SbF6)2.5XeF2,the first Xe" compound with barium. The bands in the vXeF region was consistent with the presence of several distinct XeF2

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3 Vibrational Spectra of Transition Element Compounds BY G.DAVIDSON

1

Scandium, Yttrium and the Lanthanides

Raman spectra of mass-selected scandium clusters in an argon matrix included bands due to Sc4which are consistent with Td symmetry. These were assigned as follows:v1 222 cm-' (al), v2 166 cm-' (t2),v3 103 cm-' (e).' Laser-ablated M atoms, where M = Sc, Ti or V, react with NH3 to give the following species trapped in an argon matrix: H2MNH and HMNH2. Assignments of IR bands for these are given in Tables 1 (Sc), 2 (Ti) and 3 (V).2Similar reactions of M atoms, where M = Sc, Y or La, with H2, gave matrix-trapped MH, MH2, MH2+, MH3, MH4- and (H2)MN2.Skeletal mode assignments, supported by DFT calculations and isotopic shifts, were proposed for all of these. Some assignments are listed in Tables 4 (Y) and 5 (La).3 High-pressure Raman spectroscopy on ScF3 gave evidence for phase transit i o n ~Variable-temperature .~ Raman data for Rb2KScF6(ScF6modes) were used to probe thermal phase transitions for this c ~ m p o u n d . ~ Raman spectra of ScCl3-CsCl melts (600 - 9OO0C,up to 25 mol% ScC13)show that the predominant complexes are scc163-and the novel species ScC1:- (characteristic vScCl 260 cm- 1).6 Ab initio m.0. calculations gave vibrational wavenumbers for scandium chloro-complexes (up to S C C & ~ - ) . ~ Raman spectroscopy was used to characterise the new lanthanide boron-rich compounds M1-xB12Si3.3-6, where M = Y, Gd - Lu; 0 \< x \< 0.5; 6 0.3.8 Vibrational data (especially Y - 0 stretching modes) were used to follow structural changes with changing composition in the Y203-Zr02system.' The compounds Bi2.,MaGeOs, where M = Y or Yb, give a Raman feature associated with M at 799 cm-' (Y) or 797 cm-' (Yb)." IR and Raman spectra were reported for M2Mn207,where M = Y, Dy, Er orYb. These were assigned with the aid of normal coordinate analyses." Raman data, together with calculations, gave assignments to vLn-0 modes for a range of lanthanide compounds, Ln3A15012.These were all consistent with dodecahedra1 coordination.12 DFT calculations for La@Cg2and Sc2@CS2gave calculated values for metal-cage vibrational wavenumbers. The lanthanumbased vibrations are summarised in Table 6.13 Coupled-cluster calculations gave vibrational wavenumbers for LaX3, where

-

~~~~~

~~~

Spectroscopic Properties of Inorganic and Organometallic Compounds, Volume 37 0The Royal Society of Chemistry, 2005

70

3: Vibrational Spectra of Transition Element Compounds

Table 1

Skeletal mode assignments for Sc iN H 3 reaction products (lcm-')

HSCNH~

GscissNH2 YSC-H YSC-NH~ Y,,SC-H

(HSC)~NH SCNH, ScNH

Table 2

om

YSC-NH

v,TiH2 v,,TiH2 vTiNH LNH3 WH3 YTi-H

TiNH3 HTiNH2

YsVH2 vasVH2 YV-NH LNH3 WH3 YV-H

VNH3 HVNH2

YH4

1673.7 1646.8 954.3 1567.2 1160.5 1582.3

Vibrational assignments for reaction products of Y and H z (lcm-')

(r2-H2)YH2 (r2-H2)2YH2 (r2-H2)3YH2 YH YH2 YH3 YH2+

1613.1 1582.1 947.6 (4hTi) 1547.7 1155.6 1531.7

Skeletal mode assignments for V + N H 3 reaction products (/em- ')

H2VNH

Table 4

1501.3 1474.0 638.1 1376.3 1148.3 875.9

Skeletal mode assignments for Ti + N H 3 reaction products (lcm-')

H2TiNH

Table 3

71

1385.1 1337 1309 1470.4 1459.8 1397.8 1385.1 1578.1 1542.1 1227.3 482.7

X = F or C1. Values were in good agreement with experiment except for v2.14Ab initio calculations gave vibrational wavenumbers for MLaX4,where M = Na, K or Cs; X = F, Cl, Br or I. It was suggested that both CZvand C3"forms could be stable.' The Raman spectra of MB6 crystals, where M = Ce, Pr, Gd, Dy or Yb, all contained bands 6200 cm-' due to motions of M with respect to the B6 octahedral unit.'6, l 7 The Raman spectrum of a Ce02/Si02catalyst included a strong band at 457 cm-', associated with the t2gstretching mode of the Ce06 unit. l8 The IR and Raman spectra of [Ln(C7H90)6]3f,where Ln = Pr, Nd, Sm, Eu,

Spectroscopic Properties of Inorganic and Organometallic Compounds

72

Table 5

Vibrational assignmentsfor reaction products of La and H 2 (lcm-')

(q2-H2)LaH2

1287.1 1235.3 ( T ~ * - H ~ ) ~ L ~1221 H~ 1211 LaH 1344.1 LaH, 1320.9 1283.0 LaH3 1263.6 LaH2+ 1439.0 1420.7 LaH41114.3

Table 6

Lanthanum-based vibrations for lanthanum/fullerene cage compounds (lcm-') a1

La@C82La@C82 La@G2 +

159 159 159

bl 20 27 31

b2

32 30 29

Gd or Dy; C7H90 = 2,6-lutidine-N-oxide, all include vLn-0 near 265 cm-' and 6 0 L n 0 near 110 cm-'.19 IR data for Zv,Mgl-,Fe2-,Nd,04,where x = 0,0.20,0.40,0.60,0.80,1.00;y = 0, 0.05,0.10, show bands near 425 cm-' from Nd and Fe octahedral sites, and near 600 cm-' from Zn and Mg tetrahedral sites2'A short-range force constant model was used to calculate vibrational wavenumbers for the perovskite NdNi03.21 Skeletal (vGdN, vGdC1) modes were assigned from the IR and Raman spectra of Gd4(02)2C&(py)10:vGdN 386 - 331 cm-', vGdCl (terminal)268,235 cm-' and (bridging) 206, 189 cm-'.22 the high-temperature Raman spectrum of Gd2(M00~)~ gave assignments to vMo-0 modes, with an empirical correlation between n and the Mo-0 bond length.23

(1)

IR and Raman spectra of [Ln111(L)4]-,where HL = (l),gave the following vLn-N mode assignments: Ln = Nd 225 cm-' (Raman), 198, 187 cm-' (IR);Yb 295 cm-' (Raman), 202, 192 cm-' (IR).24The IR spectrum of [YbCd(py)2]includes vYbCl at 236 cm-' and a deformation mode at 134 ~ m - ' . ~ ~ 2

Titanium, Zirconium and Hafnium

Earlier reference has been made to vibrational studies of H2TiNH, TiNH3, HTiNH2$ and the Y203-Zr02system?

3: Vibrational Spectra of Transition Element Compounds

73

DFT calculations have been reported for the vibrational wavenumbers of the cluster Ti8C12.The results for C3" symmetry were in good agreement with experiment.26Similar calculations gave predicted wavenumbers for skeletal modes of M(N3)4,where M = Ti, Zr, Hf and Th.27The complex (2), and related species, show vTiN bands in their IR spectra, near 700 cm-1,28

A mixture of C2H2and 0 2 reacts with laser-ablated Ti atoms in an argon matrix to form OTi(OH)CCH, with vTi=O at 1005.1 cm-' (963.0 cm-' for The complex [Ti2(02)2(~it)2]4-, where cit = citrate, has vTi-(02)at 606 where M = Ti, cm- 1.30 Skeletal mode assignments have been made for M(a~ac)~, V, Mn or Co, based on IR results and DFT calculation^.^^ The dinuclear complex (18-crown-6)Cl3Ti(p,-O)TiCl3(18-crown-6)has v,,Ti-0vTiCl modes Ti at 775 cm-' in the IR spectrum. For C&Ti(pL-(l8-crown-6))TiC&, are seen at 383 and 397 ~ m - ' TiC12(k3-bdmpzdta)(OMe), .~~ where bdmpzdta = bis(3,5-dimethylpyrazol-l-yl)dithioacetate,has vTiO at 635 cm-', and vTiCl at 326 cm-' in the IR spectrum.33 IR and Raman spectra were used to characterise Ti02 nanoparticles formed by hydrolysis of aqueous Tic&solutions. The Raman spectrum showed anataselike features at 160,407 and 613 Similarly, the Raman spectra of Ti02 thin films produced by CVD from TiC&/EtOH show that there exclusively in the anatase form.36 Micro-Raman spectroscopy was used to follow phase transitions with increasing strontium content in Cal-,Sr,Ti03, where 0 < x < l.37Variable-temperature Raman spectroscopy was used to monitor the phase transitions of SrTiI803. Below 24 K, two characteristic new features were seen at 170 and 545 Similar experiments were performed on BaTi03 nanocrystals;40PbZro.5T&.s03;41 and Pb(Z~1,3Nb~/3)0.~ 5Ti0.08503 cryst a l d 2 Ultraviolet Raman spectroscopy was used to probe the titanium coordination environments in some novel mesostructured titano~ilicates.4~ IR and Raman spectra were used to examine the structural and electrical properties of BaTi409 incorporated in a ZnO-B203 phase.44 The polarised Raman spectrum of CaCu3Ti4012single crystals included the following characteristic bands: 292 cm-' (t,), 445 cm-' (a,), 499 cm-' (e,), 511 cm-' (a,) and 575 cm-' (t2g)!5 The FTIR and Raman spectra of a large-pore framework sodium titanium silicate catalyst (AM-18) show the presence of five-coordinate titanium (vTi = 0 899 ~ m - ' ) The . ~ ~IR spectra of samples from the Si02-Ti02-Ge02system include features due to Ti-0-Si ~ n i t s . 4Raman ~ spectroscopy was used to identify such units in a cubic p-0x0 Si-Ti complex in a silica matrix.48Raman spectroscopy was used to characterise W-Ti-0 thin film gas sensors prepared by sol-gel dip coating.49

74

Table I H2MNH MNH3 HMNH,

Spectroscopic Properties of Inorganic and Organometallic Compounds

Skeletal mode assignmentsfor M M = YsMH2 vasMH2 vM-NH WH3 vM-H

+ N H 3 reaction products (lcrn-')

Zr 1556.0 1520.3 889.2 (90Zr) 1156.0 1478.4

Hf 1614.7 1590.9 898.3 1158.8

The IR and Raman spectra of TiC162- in [Me2NH2]2[TiC16] suggest that the local symmetry is reduced from O h to D 4 h by N-H . . . Cl hydrogen b~nding.~' Laser-ablated M (= Zr or Hf) atoms react with NH3 to form a number of products, trapped in an argon matrix. Some assignments for HZMNH, MNH3 and HZrNH2 are summarised in Table 7.5' vZr-H-Zr in [(C~~zr)~(p-H)](pH)2AlX2,where X = C1, Br or I, occurs as an IR band in the range 1309 - 1315 cm - 1.52 Ab initio calculations gave predicted vibrational wavenumbers for Zr(BH4)4. 53

(3)

The IR and Raman spectra of [ { ( P ~ N ~ ) Z ~ } & L - ~ ~ :where ~ ~ - NP2N2 J], = PhP(CH2Si-Me2NSiMe2CH2)2PPh, contain a Zr-Zr stretch of the unit (3) at 295 cm - 1 54 Variable-temperature Raman spectra of 10%Ce02-Zr02was used to probe the t + rn phase transition of Z r 0 2 at 153 K.55The IR spectra of M0.5Zr2(P04)3, where M = Mg, Ca, Mn, Co, Ni, Cu, Zn, Sr, CD or Ba, contain bands characteristic of corner-sharing ZrO6 octahedra and PO4 tetrahedra.56vZr-0-Si modes were seen in the IR spectra of Cp2Zr(OSiFc2)20(950 cm-') and [Cp2Zr(OSiFc2)0I2(944 cm-'), where Fc = f e r r ~ c e n y lRaman . ~ ~ spectroscopy was used to follow the reaction of Zr(OiPr)4and methacrylic acid (HOMc), to form Zr6(OH)4(O)4(OMc)12.Bands due to Zr-0-Zr modes were seen at 192 and 250 cm-' for the product.58 The complexes ZrC14[MeE(CH2),EMe], where E = S or Se, n = 1 or 2, have vZrCl in the range 363 - 366 cm-' cm-'. For the eight-coordinate species MC14(L-L)2,where M = Zr or Hf, L-L = MeE(CH2),EMe,vMCl bands were near 300 cm-l (Zr) or 280 cm-' (Hf).59 Ab initio calculations of vibrational wavenumbers for Hf(BH4)4skeletal modes show that experimental data are consistent with T symmetry?' Nanotubes of HfS2 give a Raman band near 350 cm-', very close to the value for the bulk rnateriaL6l

3: Vibrational Spectra of Transition Element Compounds

3

75

Vanadium, Niobium and Tantalum

Earlier reference has been made to vibrational studies on H2VNH, HVNH2, VNH3: the V205-Ce02-Si02 system;18V ( a ~ a c ) ~and ; ~ lPb(Z~1,~Nb2,3)0.~~~Ti~.~~~ The resonance Raman spectra of the argon-matrix isolated species VM, where M = Fe or Co, show Y values at 459 cm-' (Co) or 423 cm-' (Fe); 2v at 916 cm-l (Co) or 836 cm-' (Fe).62IR and Raman data have been reported for V(CO)6(and its all-I3C isotopomer). Skeletal mode assignments are shown in Table 8.63The complex (4) has an IR band due to YV-N at 605 c111-l.~~

Bu'

I RU'

There is matrix-IR evidence for the formation of C13V(CH3)0C(0)CH3by the reaction of OVC13 with (CH3)2C0in an argon matrix at 14 K. The following assignments were proposed: YV-0-C891 cm-l, ~asVCl3478 cm-' and v,VC13 419 cm-l .65 Co-deposition of OVF3and NH3 in an argon matrix at 14 K produced the complex OVF3.NH3, with YV= 0 1040cm-l, ~ a s V F 748 3 and 724 cm-', vsVF3 670 ern-'? The matrix IR spectra of the reaction products of OVC13 and 02CrC12with cycloalkyl-amides showed the formation of 1 : 1 complexes. There was also evidence for the formation of C12V(0)N(H)C3H5 and ClCr(0)2N(H)C3H5.67 There is IR evidence for the formation of VOCh- and V02C12- in aqueous HCl solutions of Vv species.68 Bands due to YV"=O (956 - 980 cm-I) were assigned from the IR spectra of [VOL]S04, where L = tetradentate ligands derived from 2,4-dihydroxy-5-acetylacetophenoneand substituted diarnine~!~The IR and Raman spectra of VO(SALIMH)(CatED), where catED = 4,5-bis(phenylethynyl)benzene-1,2-diol and SALIMH = 4-(2(salicylideneamino)ethyl)imidazolyl, contain YV= 0 at 955 cm-' and Table 8

Vibrational assignments for V(CO), (lcm-') 598.0/529.2 439.3 457.5/433.2 328.0 397.9 312.2? 348.8 95 102.2/90.3/85.5

76

Spectroscopic Properties of Inorganic and Organometallic Compounds

v,VO(CatED) at 556 c11l-l.~' The complex (5), and related species, where 0-N-S = dianion of S-methyl-3-(5-R-2-hydroxyphenyl)methyldithiocarbazate, have two v V = O bands, in the range 840 - 960 cm-1.71For VO(L)(Lcyclic), (6), has vV = 0 at 960 cm-' .72

/

MeS

The complex V1VO(sal-L-ala)(H20),where sal-L-ala = N-salicylidene. ~ spectroscopy ~ was alaninate, has vV" = 0 in the IR spectrum at 996 ~ m - ' IR used to characterise species formed by V 0 2 +ions immobilised on a mesoporous silica surface during, e.g. hydroxylation of aromatic hydrocarbon^?^ The values for v V 0 in [VO(L)2]2-, where H2L = 1,2-benzenethiol-3,4-toluene-dithiol or 3,6-dichloro-1,2-benzenedithiol,are 903 - 9 17 cm- l. These low wavenumbers for a formally V.0 unit were ascribed to hydrogen-bonding to the HNEt3+ Raman spectra (vV0) at variable temperatures and pressures for (VO)2P2O7 gave evidence for phase transition^.^^ The complex (V'VO)2(p-OH)(p-OAc)(pH2m~g-S,S)~(bipy)2, where H3mpg = a sulfhydryl-containing pseudopeptide, has vV = 0 at 964 The dianion [ ( ~ ~ ~ ) ~ ( has ~ ~IR )bands ~ ~due( to~ ~ ~ ) v V = O at 982 cm-', v U = O at 862 cm-', together with v I 0 modes near 756 cm- 1 78 The complex [enH2][(V'vO)2(VvO)02(Se03)3]gives IR bands due to the vanadium polyhedra in the range 818 - 619 ~ m - ' IR . ~ bands ~ at 1138,1063,1023 and 995 cm-' all have contributions from v V 0 and nPO for (vo)4(4,4'11H20,vM = 0 (M = V, b i ~ y ) ~ ( H P 0 ~For ) ~ [(Vv04)MoV'12036(V1V0)6]-[OH]9. .~' Mo) bands were seen at 958 and 903 cm-', with vM-0-M 694,606 cm-1.81 Ab initio and DFT calculations have been reported for the vibrational wavenumbers of V02X2-, where X = F, C1, Br or I.82The FTIR spectrum of V02(H20)(Q),where Q = 8-hydroxy-quinolinate, gave assignments based on ab initio calculation^.^^

3: Vibrational Spectra of Transition Element Compounds

77

The cis-V02 unit in (7), where X = N or CH, gives two IR bands in each case (899 - 946 ~ m - 9 . Similar ~~ features (at 895 and 918 cm-') confirm the cisgeometry for the V 0 2 fragment in [VOz(salhyph)]-, where Hzsalhyph = (8).85I n situ Raman spectroscopy was used to help identify the vanadium complexes present in supported molten salt catalysts for SO2 oxidation, e.g. vvo@04)23-.86 The IR and Raman spectra of [(V02)2(4,4'-bipy)o.5(4,4'-Hbipy)(P04)].H20 gave the assignments shown in Table 9.87 Stretching modes, vV04, were assigned from the IR spectra of samples in the LaV04-Nb205-Ta205system. In solid solutions LaNb2-2,Ta2,V09athere was evidence for two types of V 0 4 unit.88The IR spectra of cubic inverse spinels LiNil..,Co,V04, where 0 < x < 0.5, show complex patterns of YVO stretching modes from the V04 tetrahedra.89 Experimental vMOt and vM-Obr-M modes were reported from the FTIR spectra of VWs0193-,cis-V2W@1:and w60192-, and assigned using DFT calculations?0The high-pressure Raman spectrum of CaV203shows that a phase transformation occurs near 9 GPa.91 IR spectroscopy was used to characterise the dimeric chloride complexes [V*03(H20)8-nCln](4-n)+ in the system VV-HCl-LiCl-H20.92 The Raman spectra of as-deposited vanadium oxide thin films include broad bands near 520 and 650 Table 9

Y W 2

YSVO2 6V02 YV-0 YV-N

Vibrational assignmentsfor (V02)2(4,4'-bipy)o.5(4,4'-Hbipy)(P04) (lcm-9 IR

Raman

943 919

939 905 325 525 342

-

52 1/400 345

78

Spectroscopic Properties of Inorganic and Organometallic Compounds

cm-', together with a sharp peak at 1027 cm-' due to vVv=O and a feature at 932 cm-' probably due to vV" = 0.93 The IR spectra of glasses in the B203-V205-Mo03gave evidence for V04,V05, There is Raman spectroscopic evidence for the formation M o o 4and B 0 3 of CeV04 by heating V205/Ce02-M02 catalysts, where M = Ti95or Zr.96The Raman spectra of alumina-supported vanadium oxide catalysts in the presence of K + included characteristic vV = 0 bands.97The high-pressure Raman spectrum of CaV205shows a phase transition at about 9GPa.98 The Raman spectrum of lithium vanadate prepared by solid-state reactions Bands included bands showing the presence of 6-, E- and y-phases of LiV205.99 due to vV = 0 (985,917,854 cm-') and vV-0-V (799,724,690,647 cm-') were observed in the IR spectrum of polymeric ([(phen)V'v0]2(VV205)(HP04)}..100 Similar types of band were also observed in the IR spectra of M(4,4'bipy)(H20)V2Se2010, where M = Co or Ni.'" Raman spectroscopy was used to characterise vanadium-oxygen species in V/Ce02 catalyst systems. There was evidence for V-0-V polymeric chains, tetrahedral surface species and V2O5.lo2 The FTIR spectra of [SiV,M O , W ~ ~ - , ~ , O gave ~ ~ ] (assignments ~ + ~ ~ - to VasM = 0, and vasM-0br-M modes.lo3In situ Raman spectroscopy (vV= 0)was used to monitor the species present on alumina-supported vanadium oxide catalysts during propane oxidative degradation.'04 The IR spectrum of (PW9V3040[Ag(bipy)]2[Ag2(bipy)3]) included YV= 0 872 cm-', v W = O 951 cm-' and vM-0-M (M = V, W) 788, 762 cm-'.'05 V407(HP04)2(2,2-bipy)2 has IR bands from v V = O at 964.8, 939.8, 889.2 and 805.6 cm-', with vV-0-V at 658.3 and 598.4 cm-'.'06 IR bands from vV-0 modes were seen at 422, 466 and 488 cm-' for [ C O ~ ( C ~ O ~ ) V ~ O The ~ ~IR ]~-.'~~ spectrum of [((H~O)Ni(enMe)~MoV~Mov1~V1v~(VvO~)O~~~2~Ni(en [Ni(enMe)2]4.8H20,where enMe = methylethylene diamine, includes YM= 0 bands at 972,955 cm-', and vM-0-M 840,675 cm-', where M = V or Mo.'Os The IR and Raman spectra of Cs4[Na2(H20)10](V10028) are dominated by decavanadate anion bands.lo9 The IR emission spectrum of VCl gave we417.4 cm-I, and O e X e 3.5 cm-l.'10 The 1:l complex OVC13.0(CH3)2showed vasVC13at 474 cm-',compared to 505 cm-' for the monomer."'

(9)

The complex (9) has an IR band from vNbN at 1333 cm-'.'12 The complex [Nb(02)2(edta02)]3-has v,Nb(02)at 646 cm-' and vNb(02) at 558 cm-'.'13 The IR spectra of MOF3, where M = Nb or Ta, include a very strong, broad band near 650 cm-', believed to be a superposition of vM-0-M and vMF(t) modes. Also, a vM-F-M bridging mode is seen at 500 cm-', together with vM = O(t) at 985 cm-' (Nb) or 1016 cm-' (Ta).l14Matrix-IR data were reported and assigned for Nb(E)X3,where E = 0 or S, X = Cl or Br. Assignments are summarised

3: Vibrational Spectra of Transition Element Compounds

Table 10 NbOC13 NbOBr, NbSC13 NbSBr3

(lcm-')

Vibrational assignments for N b ( E ) X j YNb = E 993 985.0 565.0 558.5

79

vNb-X (e) 448 341.3 439 330.0

vNb-X (al) 400 393

(argon matrix data) in Table A Raman band at 850 cm-' for Bi4Ti3.,Nb,012ceramics is sensitive to Nb substitution, and presumably involves N b - 0 motion.' 16. The Raman spectrum of (K20)15(Nb205)15(Te02)70 glass included bands due to vNbO modes of niobate polyhedra at 450 and 890 ~ m - ' . ' ' ~Raman spectra from the Bi203-Zn0-Nb205 system show that vNbO and vZnO modes change little with changing composition.l'* IR data have been reported and assigned for several niobium oxide cluster cations (from IR multiple photon dissociation spectroscopy). Thus, Nb206+,(10) has terminal Nb = 0 stretching bands at 998 and 1007 cm-', while (11)shows such features at 997 and 1013 crn-'.'19 0

\

IR spectra of melts in the K-Nb-S system include bands due to Nb2Sl14-.120 The complexes NbC12(dpmpza)(RC.CR'),where dpmpza = (3,5-diphenylpyazoll-yl-3',5'-dimethylpyrazol-l-yl)-acetate; R = R' = Me or %Me3;R = Ph, R' = Me or Et, all give two vNbCl IR bands, near 330 and 370 crn-'.12' vNbCl bands in (12), where R = H, Me, %Me2, 'Pr or PPh2, all lie in the range 254 - 307 cm-l

122

The IR and Raman spectra of [{Ta(Se&(Se))2SeI4- gave assignments to a range of skeletal modes, including vsTaSe 276 cm-l, and vasTaSe281 cm-'.'23

80

4

Spectroscopic Properties of Inorganic and Organometallic Compounds

Chromium, Molybdenum and Tungsten

Previous reference has been made to vibrational studies on Gd2(Mo04)3;23 ClCr(0)2N(H)C3H5;67 [(VV04)M~V112036(V1V0)6] [0Hl9.11H20;*'the B2o3-V2O5M o 0 3 sys [{ (H20)Ni(enMe)2 - MoV4MoV14VTV8( VVO4)040)2 { Ni(enMe)2)] [Ni(enMe)2]4.8H20;'08 W-Ti-0 thin films;50 and (PW9V3040[Ag(bipy)]2CAgz(bipy)31).' 0 5 The IR spectrum of Cr2(OH2)2(p-formato)4gave assignments to skeletal modes, based on a normal coordinate analysis. These included 537 cm-', vCrCr/GCr-Cr-0; 540 cm- vasCrOO/Ga,C-O-Cr;464 cm- ' ~ ~ , C r 0 0 / 6 , , , . 'The ~~ resonance Raman spectrum of mass-selected CrFe in an argon matrix showed a progression in v, from which it was calculated that We = 166.6 0.8 cm-', and Wexe = 1.1 0.1 ~ m - ' . ' ~ ~ Laser-ablated Cr atoms reacted with H2/D2 mixtures to give a range of matrix-trapped products, identified by IR spectroscopy. In a neon matrix, (H2)2CrH2gave vCrH at 1529.5 cm-' (vCrD 1112.1 cm-' for (D2)2CrD2). There was also evidence for CrH, (H2)CrH,CrH2 and (H2)CrH2,together with deuterioanalogues.'26The species HCrCCH was formed by a Cr atom + C2H2reaction, and trapped in an argon matrix; it gave an IR band from vCrH at 1670.1 cm-' (1204.4 cm-' for the D a n a l ~ g u e ) . ' ~ ~ Ab initio calculations gave predicted vibrational wavenumbers for Cr(H20)63f.128 The IR spectrum of CrOzC12(biq), where biq = 2,2'-biquinoline, shows vCr02 at 952,946 cm-', 6Cr02439 cm-' and vCrC12386 ~ m - ' . Raman '~~ spectroscopy was used to characterise Cr0,/La203model catalysts - bands at 864, 884, 913 and 921 cm-' were ascribed to La2Cr06.'30The complex cation [U02(Cr04)(I03)2]2+ has I R bands from C r 0 4 at 956, 943 and 873 cm-', with vUOz bands at 902 cm-' (antisymm.) and 831 cm-' (~ymm.).'~' SERS data (vCr0) were used to characterise monolayers formed from chromate corrosion inhibitor on copper surfaces.'32 High-pressure Raman spectra of MgCr204(to 76.4 GPa) showed that a sluggish phase transition occurred over the pressure range 14.2 - 33.1 GPa.'33In situ high-pressure Raman spectroscopy of NiCr204showed that dissociation to Cr203and NiO began at 13.1 GPa. The process was reversible on raising the pressure to 57.1 GPa and returning to 33.3. GPa.'34 Ab initio calculations on M02 suggest that for the ground state 03, should lie in the range 450 - 486 cm-' cm-'. The observed band at 394.5 cm-' is probably due to the 3C+,state of Mo2.13' The complex Mo4(PFT), i.e. [(tBuC02)3M02(p02CC6F4C02)Mo2(02CtBu)3], gives a strongly enhanced resonance Raman band at 399 cm-', due to ~ M 0 M o . l ~ ~ Skeletal mode assignments for CpMo(C0)3Cl and (C5R5)Mo(0)2C1,where R = H, CH3or CH2C6H5, are summarised in Table 1l.i37 Skeletal mode assignments were proposed from IR spectra of complexes of nicotinic acid (H2nico)with Mo, Re, Pd and Pt. For [M0~06(Hnico)~]~-, v,M002 is at 931 cm-I, vasM002at 879 cm-' and vMoN at 455 ~ m - ' . ' ~ ' The resonance Raman spectrum of the sulfo-form of cow's milk xanthine oxidase has vMoV1=0 at 899 cm-' (892 cm-' for the desulfo form), together with

3: Vibrational Spectra of Transition Element Compounds

81

Table 11 Skeletal assignmentsfor some CpMo derivatives (lcm-')

vMoCl VasMOCP v,MoCp oM002 TMoO~ 6M002

281 358 337

396 353 329 263 238 375

398 393 373 349 273 243

382 335 305 250 226 372

vMoV1= S at 474 cm-' (32S)or 462 cm-' (34S).'39 The IR spectra of [M(CN)4(0)py]2-,where M = Mo or W, contain vM = 0 at 963 cm-' (M = Mo) or 960 cm-' (W).14' The IR spectra of transR(Cl)MoO(NNPhR')(o-phen). where R = R' = Me or Ph; R = Me, R' = Ph; R = Ph, R' = Me, all have ~ M =o0 in the range 880 - 900 cm-'.14' The cis-MoO;+ unit in cis-Mo02(L),where H2L = N', N"-bis(2-hydroxy-3,5dimethyl-benzy1)-N,N-dimethylethylenediamine, has vasMo= 0 at 925 cm-', vsMo = 0 at 902 c 1 ~ 1 - l .Mo02L(L'), '~~ where H2L = anthranilhydrazide, L' = MeOH, py, 4-Mepy, imidazole or 1-Me-imidazole, all show two vMoO IR bands (912 - 929 cm-', 898 - 914 ~ r n - ' ) . ' ~ ~ IR and Raman spectra of M o O ~ ( C H ~ ~ ~where CS)~ H2CH2nicS , = 2-mercaptonicotinic acid, have vSM0O2932 cm-', vasMo02903 cm-', with a feature that may be vMoOMo at 762 cm-'.l4 The cis geometry for M02(L")C1,where M = Mo, W; HL" = 2-N-(2-pyridylmethyl)aminophenoland N-alkyl derivatives, gave two v M 0 2 IR bands, as expected.'45Skeletal mode assignments are summarised in Table 12 for M(pyz)(H20)2M002F4,where pyz = p y r a ~ i n e . ' ~ ~ The Schiff-base complexes [Mo02L],, where L = O,O,N-tridentate Schiff bases, have ~ M =o0 at 920 cm-', ~ M =o0 . . . Mo 780 ~ m - ' . The ' ~ ~IR spectra for M(Mo02)(103)4(0H),where M = Nd, Sm or Eu, gave assignments to vMoO (e.g. for M = Nd, 933, 887, 876 cm-I), with vMo-OH 1066 cm-'.14* The IR and Raman spectra of M o o 3thin films on silicon substrates (prepared by CVD of Mo(CO), + 02) show that they are a m o r p h ~ u s .IR ' ~ ~and Raman spectra of (R3Sn)2M004,where R = Me, "Bu, Cy, Ph or Bz, gave assignments to vMoO and 6 M o 0 modes, e.g. for R = Me, 856 cm-' (IR), 917, 867 cm-' (YMoO),348, 311 cm-' (6Mo0) (Raman).15' High-pressure Raman spectroscopy of K s c ( M 0 0 ~ showed )~ that an irreversible structural phase transition occurred near 2.0 GPa.I5l Two-dimensional Raman correlation spectroscopy was used to characterise sodium molybdate structures that include and are intermediate between hexagonal and orthorhombic forms.'52

Table 12 Skeletal assignmentsfor M(pyz)(H20)2Mo02F4 (lcm-') ~

M = Y,MoO~ V,SMOO2 vMoF

Zn 952 909 568

Cd 954 913 547

82

Spectroscopic Properties of Inorganic and Organometallic Compounds

The IR spectra of Mo204L2D2,where L = P'-hydroxy-P-enaminones, D = ROH (R = Me, Et or Pr) all show ~ M =oO(t) near 950 cm-', vMo-O(br) near 730 c ~ l l - ' The . ~ ~IR ~ spectrum of [ M o ~ O ~ ( C ~ Oincludes ~ ) C ~ ~~ ] M ~ =o0 bands at 965 and 943 cm-' and vMoCl316 c111-l.'~~ The complex [La2(DNBA)4(DMF)8][Mo6019], where DNBA = 33dintrobenzoate, has vMo-0-Mo at 802 cm-', v M o = O at 959 cm-' from M o ~ O ~ ; - Some . ~ ~ ~similar assignments were also proposed from the IR spectrum of the [(DBl 8C6)Na(H20)1,5]Mo6019.CH3CN.156 The IR spectrum of [Me2NH2]3[PMol2O40]includes vMoO(d) 964 cm-', vMo-O(b)-Mo 865 cm-', and vMo-O(c)-Mo 777 cm-', showing that the ion retains the Keggin struct ure.157 Raman spectroscopy was used to characterise MoS2 prepared from MoC15 and he~amethyldisilathione.~~~ Skeletal (metal cluster) modes were assigned from the Raman spectra of C~,MO,F~(S)(T~)(CO)~, Cp2M02Fe(S)(CO), and C~,MO~F~,(T~)~(CO),.'~~

The Raman spectrum of I ~ ~ ~ - W ( C O ) ~ ( M ~ ~ P C ~=HCH2) ~ P includes M~~)(~~-S bands due to the unit (13) at 785 and 422 cm-' (755, 406 cm-' for the CD2 analogue).160 The Raman spectrum of W(N2(NCEt)(dppe),shows vW-N2 at 462 cm-' (444 cm-' for 15N2).161The IR spectrum of [WF(NNH3)(depe)2]2+,where depe = 1,2-bis(diethylphosphino)-ethane,has vWN at 570 cm-' (557 cm-' for I5N), GWNN at 436 cm-1.162A band assigned as vW-P was seen at 201 cm-' in the Raman spectrum of [W{P(CF3)2}(CO)5]-.'63 An IR band at 942 cm-' was assigned as v W = O for Cp*(O,(O)W-C.)CC.CH.164Ab initio calculations have been made on the effects of pressure on the vibrational spectrum of wo3.'65IR spectroscopy was used to characterise W 0 3 films prepared by thermal evaporation (vW = 0,YO-W-0 and vO-H modes).'66 FTIR and Raman spectra were used to study electrodeposited W 0 3 films.'67 Characteristic Raman bands were reported for tungsten oxide nanowires.16' The Raman spectra of tungsten oxide films prepared from W(OAr)6 precursors included bands at 807, 715, 273 and 133 cm-1.169IR and Raman spectra were used to probe the structures of porous W03 films templated with a sol-gel organic-inorganic hybrid.17' The Raman spectrum of a polycrystalline tungsten oxide film shows that W6+ is reduced to W5+with Li+ and electron intercalation.17' IR and Raman spectra gave structural characterisation of nanosize Ti-W mixed oxides with an anatase structure (chiefly using vW = 0 near 970 ~m-').',~ IR bands due to vW = 0 (980, 1014, 1021 cm-') were used to follow structural effects for W03-Zr02 catalysts on exposure to H2.173Raman spectra of

3: Vibrational Spectra of Transition Element Compounds

83

W03/Nb205samples gave evidence for surface W03,microcrystalline W 0 3and other surface species (not ~pecified).'~~ IR data (YWO)were used to characterise (1-x)Te02.xW03glasses, where 0 ,< x < 0.325.175The Raman spectra of tungsten-bearing goethite and haematite minerals include a broad band in the range 580 - 750 cm-I due to W - 0 self-assembled ~ 1 u s t e r s . l ~ ~ High-pressure Raman data of CaW04 (to 65 GPa) gave evidence for phase transitions at 12, 40 and 45 GPa.177Similar experiments on SrW04 revealed a pressure-induced phase transition starting at 11.5 GPa.178Variable-temperature Raman spectra for KSC(WO~)~ showed that three thermal phase transitions occurred in the range 100 - 294 Variable-temperature and -pressure Raman spectra for KNbW209 showed that the known phase transitions at 523 and 543-553 K led to very few spectral changes. The 290- 350 K phase transition was shown to involve tilting of W 0 6 octahedra.lgO IR and Raman spectra (YWO, YWOW) were used to characterise = 1 or 2."' The complex [ A s V ~ W ~ ~ . ~ O ~ ~ ] ( where ~+')-, x [Fe"'(OH2)2Fe"'2(As~wl~o~6)2]'2has YW= O(t) at 937 cm-', and two bands due to Y W - O ~ ~ ~Characteristic ~ ~ ~ - W .Y ~W ~ -~0 features were identified in the Raman spectrum of the polyoxoanion [EU(H~~)~(CC-~-PZWI~~~~)]~occluded within O)]'~- a modified MCM-41.Is3 The Raman spectrum of [ A S ~ W ~ @ ~ ~ ( H ~ includes YWOband at 972 cm-1.184 The Raman spectra of WS2 nanotubes confirm their stability to shock at shear stresses of up to 21 GPa.'" The Raman spectrum of WS2 formed from W(CO)6, wOc4 or WC16 and HS(CH&SH or HSC(CH3)3 shows bands at 416 and 351 cm-l .186 TheIR spectra of [(RS)WS3]-, where R = n-hexyl, C1CH2CH2CH2CH2, (14) or (15),all include YW= S bands in the range 488 - 493 cm-', YW-SR 413 461 cm-'.lg7

A high-resolution FTIR study of WF6 under continuous supersonic jet expansion in the v3 region gave the measured band centres for the different isotopic species shown in Table 13.1g8

Table 13 Band centresfor v3for WF6isotopomers (lcm-') lS2WF6 lS3WF6 'S4WF6 lS6WF6

714.538 19 714.21406 713.89544 713.26621

84

5

Spectroscopic Properties of Inorganic and Organometallic Compounds

Manganese, Technetium and Rhenium

Earlier reference has been made to vibrational studies of M2Mn207;11and Mn(a~ac)~.~~ Laser-ablated M ( = Mn, Re) atoms react with H2to give MH,, where n = 1,2 (Mn), 1,2,4 (Re).IR bands due to vMH bands were assigned using isotopic shifts, e.g. v for MnH 1477.9 cm-' in an argon matrix (1066.0 cm-' for MnD).lg9 IR and Raman spectra gave skeletal mode assignments for MBr2L2,where M = Mn, Co or Ni, L = rn-methylaniline, e.g. for the polymeric Mn complex, vMnN bands were at 419, 331 cm-', vMnBr 192, 167 cm-' (all bridging). For monomeric CoBr2L2,vCoN bands were at 420,399, vCoBr(t) 234,210 ~ m - ' . ' ~ ' Manganese atoms react with 02/Ar mixtures to give matrix-trapped MnO (v 833.3 cm-' for l60,796.8 cm-l for "0)and MnOz(816.4 cm-' for l60,775.3 cm-' for "0).Evidence was also found for Mn02- and MnO4-.'" There is resonance Raman evidence for the formation of a stable manganese(V)-oxo corrolazine complex (16) (R = 4-tBuC6H4),with vMn = 0 979 cm-' (938 cm-' for 180).192 R

I

R

I

R

The Raman and IR spectra of Lio.3Mn02include bands due to M n 0 6 modes which are significantly different from those in M n 0 2it~e1f.I~~ The Raman spectra of MMn03,where M = La, Pr, Nd, Tb, Ho, Er, Y or Ca, contain features due to the structural configurations of M n 0 60 ~ t a h e d r a .IR I~~ spectra of Lal-,Ca,Mn03 show characteristic wavenumber shifts with increased x for the MnO stretch (near 600 cm-') and OMnO bend (near 400 ~m").''~ Characteristic v M n - 0 bands were seen in the IR spectra of Lao,~-,Bi,Cao,~Mn03, where x = 0,0.05,0.1, 0.15, 0.2 or 0.25.'96Raman spectroscopy was used to probe structural changes during the charge-ordering transition for Pro.5Cao 4S~o.~ Mn03.197 IR data were reported for Mn04- in KC1O4 matrices, giving harmonic wavenumbers for components of v3, i.e. me927.9,932.7,960.1 cm-'.19' There is IR evidence for hydrogen-bonding between Mn04- and NH3 ligands in [CU(NH~)~] High-pressure Raman data showed phase transitions in layered manganites, Lao.5Sro.sMn04 and Sr2Mn04.200 The IR spectrum of C00.6Zno.4MnxFe2-x04 includes vMnO at 441 cm-'. The tetrahedral and octahed-

3: Vibrational Spectra of Transition Element Compounds

85

ral FeO stretches were seen at 569,389 cm-' respectively.201 The FTIR spectra of LiMn204 and LiMxMn2-,04,where M = Mg or Cu, included vMnO modes near 600 and 525 cm-' (the latter also having a contribution from vLiO).202Another report of the IR spectrum of LiMn204 gave assignments of v,,MnO of MnIV06(618.6 cm-') and of Mn"'06 (501.5 ~ m - 9 . ~A' third ~ report on this compound merely suggested that M n 0 6 modes lay between 450 and 650 cm-1.204 Raman spectra of thin-film Lil-xMn204 electrodes include a band at 592 cm-' characteristic of h-Mn02.The data suggest that each value of x possesses its own electronic band The Raman spectra of spinels Lil +x+zMn2-z04, where 0 < x < 1; 0 < z < 0.33, gave evidence for trigonal distortion of MnO6 octahedra by lithium ion insertion.206The Raman spectra of spinels AMn204, where A = Mn, Mg or Zn, were analysed in terms of M n 0 6 and A 0 4 vibrat i o n ~ The . ~ ~high-pressure ~ Raman spectrum of CaMn204,to 73.7 GPa, gave evidence for structural t ransformations.208 Skeletal mode assignments were reported for [Mn4O6(bpea)4]"+,where bpea = N,N-bis(2-pyridylmethyl)ethylamine, n = 4 (Mn:') or 3 (Mn'"Mn3'V).Assignshifts and normal coordinate analyses.*09Skeletal ments were based on 160/180 modes assignments were also proposed from the Raman spectra of [(C6HlSN3)6Fe8(~3'o)2(~2~0H)l~]M~I~OI~(OAC)I~(H (vMnO) ~ O ) ~ and Br7.(H20)Br(vFeN, vFe0).210 R

The complex trans-[TcNC12(Ph3PNH)2] has an IR band due to vTc=N at 1065 .211 The IR spectra of complexes (17), where M = 99Tc,R = Me (917 cm-'), OMe (913 cm-'); M = Re, R = Me (942 cm-'), OMe (938 cm-'), gave the assignments to vM = 0 noted.212The IR spectrum of 99gT~O(L)Cl, where H2L = (2-C5H4NCH2NHC0)2CH2, has vTc = 0 at 945 cm-', vTcCl at 374 cm-I. For ReO(L)OEt, vRe = 0 is at 934 ~ r n - ' The . ~ ~Raman ~ spectrum of AgTc04 shows vTcO modes at lower wavenumbers than for the potassium The complexes [(ReH(NO)L(PPh3)2)2(p-HN = NAr-ArN + NH)I2+,where L = P(OEt)3, PPh(OEt)2,Ar = Ph or 4-MeC6H4,all have IR bands from vReH in the range 1850 - 1900 For [(THF)C&Re=N-PdCl(p-Cl)]22-, vReN is at 1126 crn-', with vPdCl(t) 348 cm-', vPdCl(br) 326 cm-1.216IR bands due to vRe-NO were seen in the range 471 - 480 cm-' for mer, cis-ReBr3(NO)(OAsPh3)2

cm-l

86

Spectroscopic Properties of Inorganic and Organometallic Compounds

and related species.217 The matrix IR spectrum of M e 4 R e = 0 in an argon matrix has v R e = O at 1016.8 cm-', v,ReC4 502.5 cm-' and vdReC4469 cm-'. For H2C= Re(0)(CH3)3, vRe=C is at 782.4 cm-' and v R e = O at 977.5 cm-'. All assignments were consistent with isotopic shift data.218Two new methyloxo-rhenium(V)complexes have been prepared: (L)Re(Me(=O), where HL = 2-mercaptoethyl sulfide or 2-mercaptoethyl ether, with vReO at 984, 997 cm-I re~pectively.~'~ Two diastereoisomers of ReO(PN2S-OMe), where PN2S-OMe = N-[N-(3-diphenyl-

1-

phosphinopropionyl)glycyl]cysteine methyl ester, have vReO at 989, 987 cm-' respectively.220 The complex (18) has an vReO band at 955 cm-1,221while (19) shows such a feature at 941 cm-'.222In (20) it is at 1003 cm-' (shifting to 951 cm-l for the ''0 analogue).223For ReOX2(L-his-N,N,O),his = histidine, X = C1 or Br, vReO is at 1008 cm-', while for [ORe(L-hisMe)X2I20,vReORe is at 695

Table 14

Vibrational assignments for (CH3)3Re02and (CD&Re02

vSReO2 vasRe02 vasRe(Cad2 v,[Re(Ca,), + Re(C,,)] v,[Re(CaJ2-Re(C,,)]

Table 15

vSReO3 vasReO3 vReC

993.9 956.3 527.0 518.9/531.7 482.6

(lcm-')

997.8 941.8 479.2 477.9/488.8 438.3

Vibrational assignmentsfor C2H5Re03and C2D5Re03(lcm-')

997.3 996.4 970.11967.3 967.0 544.31540.71537.8 489.31485.9

3: Vibrational Spectra of Transition Element Compounds

87

The IR spectra of matrix-isolated Me3Re02,and (CD3)3Re02 gave the skeletal mode assignments listed in Table 14.225The IR spectrum of matrix-isolated C2H5Re03gave the assignments shown in Table 15, backed up by DFT calculations.226IR and Raman spectra gave skeletal mode assignments for polymeric { Re03(C104)},,including v,ReO(t) 1001 cm-', v,,ReO(t) 975 cm-'.227 where P-P = dppe, dppp, M = Mn The complexesfac-(OC)~(P-P)MORe0~, or Re, show two vReO bands in the region 900 - 955 cm-'.228 IR bands for vRe = 0 for (21) were seen at 930 and 942 cm-', compared to 958,1005 cm-' for free MeRe03. The shifts are consistent with the donor capacity of the pyridine derivative.229The species Re2(0)3(L)2(P)2, where P = PMe2Ph, HL = (22) and related, have vRe = 0 910 - 945 cm-' and 894 - 912 cm-', vRe-0-Re near 670 cm - 1 230

The complex (23), where Cp' = Me4EtC5,has an IR band at 486 cm-' from The Raman spectrum of the cluster [Re6S8C16]4- includes algbands at vRe = s?31 222 cm-' (C&),304 cm-' (Re6)and 428 cm-' (Ss),together with weaker e, and t2g Raman-active

6

Iron, Ruthenium and Osmium

Earlier reference has been made to vibrational studies on ZnxMgl~,Fe2.yNdy04;20 VFe;62; CrFe12' CpzMo&( S)(Te)(C0)7 and related;' 59 ~Fe"'(OH2)2Fe'112(As2w~~056)2]2-;182 and C O ~ . ~ Z ~ ~ . ~ M Y ~ F ~ ~ - , ~ ~ Iron atoms and C O trapped in an argon matrix form Fe2C0,which gave the skeletal mode assignments shown in Table 16.233Nuclear resonant inelastic X-ray scattering (NRIXS) gave evidence for Fe-H(D) modes, e.g. collective modes of FeH2- units in [57FeH(D)6][MgBr-(THF)2]4.234 Skeletal mode assignments were proposed from the IR spectra of [Fe(N2)(X)(depe)2]+,where depe = 1,2-bis(diethylphosphino)ethane,X = H or Cl - Table 17. The assignments were based on isotopic shifts and ab initio calculation^.^^^ The resonance Raman spectrum of the haem a3-C.N-CuB2+complex of

Spectroscopic Properties of Inorganic and Organometallic Compounds

88

Table 16

Vibrational assignments for Fe2C0 (lcrn-')

483.2 37 1.6 291.5

vFe-CO GFe-C-0 vFeFe

477.8 361.2 290.7

471.1 368.1 291.2 ~

Table 17

X

_

_

_

_

~

Vibrational assignments for [Fe(NZ)(X)(depe)z]+ (lcm-')

HvFeN GFeNN vFeH GFeH X = ClvFeN GFeNN =

~

14N/'H

lSN

D

479 487 1877 783 503 5181512

472 482 1876 783 494 494

479 <479 1355 5741583

oxidised cytochrome aa3 oxdase includes a band at 488 cm-' due to the Fe-C=NCuB stretch and another at 406 cm-I due to the equivalent bending mode.236 Resonance Raman data for CO-adducts of the YC-1 benzamidazole compound include vFe-CO at 488 cm-' due to the six-coordinate CO-haem, and at 521 cm-' due to the five-coordinate haem.237Similar data were given from resonance Raman spectra of the haem protein CooA of Rhodospirilium r~brum;2~* and from the Q360 mutants of cytochrome P450,, from Pseudomonas pulida in the Fe"-CO form.239 Ion-implantation in a-Si:Fe thin films produces iron silicide (f3-FeSi2)with FTIR bands at 263,293,308,345 and 475 cm-'.240 A resonance Raman band due to vFe-His was seen at 214 cm-' for the photo-dissociated CO-complex of wild-type direct oxygen-sensing protein from E. ~ o l i . The ~ ~ ' temperature dependence of vFe-L (L = imidazole and substituted derivatives) was reported from the resonance Raman spectrum of mutant H93G myoglobin, showing some coupling with low-wavenumber haem doming motions. For L = 1-MeIm, vFeL is at 238.6 cm-' at lOOK, 229.2 cm-' at N293K.242Proximal ligand motions in the same mutant were probed by resonance Raman spectroscopy in the same spectral region.243 F T Raman spectra of self-assembled molecular films of tetra-amino metal (Fe, Co, Cu) phthalocyanines included a band at 236 cm-' due to vM-N, where N is from the NH2group on the phthalocyanine molecules.244 Bands due to vM-N(Pc) were assigned from IR spectra of M ( p ~ ) ( p y )where ~ , M = Fe (331 cm-') or Co (312 cm-'). For M = Fe, the mode is 23 cm-' higher than in M(Pc), while for M = Co there is very little shift.245 A resonance Raman spectral study of NO-binding at the mononuclear active site of reduced pyrococcus furiosus superoxide reductase, showed vFe-NO at 475 cm-' and vFe-S(cys) 291 cm-'.246TRIR data gave assignments to vFe-NO and GFe-N-0 for the ground state (GS) and two metastable states (MS1, MS2) for [Fe(CN)5N0]2-, Table 18 (assignments based on DFT calculations, isotopic

3: Vibrational Spectra of Transition Element Compounds

Table 18

vFe-NO GFe-N-0

89

Vibrational assignmentsfor [Fe(CN)jNO]'GS

MS 1

MS2

657 667

565 582

547 596

(/cm-')

shifts).247Resonance Raman data on NO-adducts of a series of myoglobin mutants show poor correlation between vFe-N and vNO wavenumbers. This was believed to be due to variability in the Fe-N-0 angle in the The IR spectrum of [Fe"'(tnpa)(0H)(CH3CO2)]+,where tnpa = tris(6-neopentylamino-2-pyridylmethyl)amine,has vFe-OH at 574 cm- 1.249 Resonance Raman data allowed direct detection of Fe'" = 0 intermediates in the reaction of H202 with cytochrome aa3 oxidase from Paracoccus denitrificans.vFe = 0 is at 804 and 790 cm-' for the two forms with different oxoferryl conformations of the haem a3-CuBpocket.250 The Raman spectrum of [Felll(L)(OOtBu)]+, where L = hydrotris(3-tertbutyl-5-isopropyl- 1-pyrazolyl)borate, includes vFeO at 625 cm-1.25' The cytochrome c oxidase model compound Fe/Cu[NMePr] porphyrin shows vFe-02at 570 cm-' on oxidation (544 cm-l for 1802).252 Two twin-coronet porphyrins (linked by imidazole (TCP-IM) or pyridine (TCP-PY))in oxygenated form show resonance Raman bands due to vFe-02at 586 cm-' (TCP-IM) or 583 cm-' (TCP-PY).253Resonance Raman spectroscopy was used to characterise human cytoglobin (cyb),e.g. vFe-02for oxy-cyb at 572 cm-', suggesting a polar haem environment ?54 Resonance Raman data for [(N4Py)Fe"'(q2-02)]+,where N4Py = N,N-bis(2pyridylmethyl)-N-bis-(2-pyridyl)methylamine, has vFeO of (24) at 495 cm- .25s PbTi03and BaTi03 doped with Fe give an IR band near 600 cm-' due to F e 0 6 octahedra, with another at 410 cm-' from Ti06.256 The complex Fe11120(Hntb)2, where H3ntb = tris(2-benzimiIR dazolylmethyl)amine, has v,,Fe-0-Fe at 834 cm-' in the IR spectra of the bridged salen complexes (25), where R' = 1,2-ethanediyl and related, R2,R3 = H, tBu, all give an IR band due to v,,Fe-0-Fe in the range 820 860 cm-'.25s +

I

\ O 0,Fe

The resonance Raman spectrum of [Fe202(5-Et3-TPA)2]3+, where 5-Et3-TPA tris(5-ethyl-2-pyridylmethyl)amine,gave assignments to bands from the CZh Fe202 core as follows: (26) 666 cm-', (27) 409 The IR spectrum of [Fe2(p-o)(p-HCo2)(N-MeIm)8]3+ includes v,Fe-0-Fe at 763 cm-' 260 High-pressure Raman studies on Fe203reveals phase transitions at 26.6, 35 and 57.5 GPa.261The IR spectrum of an 10Ba0.40Fe203.50P205 glass shows vFeO bands at 637 and 593 cm-'.262In situ high-pressure Raman spectroscopy of =

90

Spectroscopic Properties of Inorganic and Organometallic Compounds

ferrite, MgFe204to 51.6 GPa shows that a phase transition occurs at 27.7 GPa.263 The IR spectra of Fe30(0Ac)3(02CR)3(EtOH)3and Fe30(02CR)6(EtOH)3, where R = C7H15,CllH23and C&1, all gave assignments to vasFe30modes.264 Raman data were reported for magnetite, Fe304to 20 GPa - no phase transitions were The resonance Raman spectrum of the five-coordinate high-spin form of recombinant human thromboxane synthase included vFeS at 350 cm-1.266Similar data for the succinate quinine oxidoreductase from Sulfolobus tokodaii gave evidence for a [2Fe-2S] cluster core.267Assignments to the same unit were obtained from the resonance Raman spectra of di-iron ferredoxins.268A [3Fe-4Slf core was identified from the resonance Raman spectrum of human recombinant holo-IRP1 (iron regulating protein I), with vFeS at 405 c1l1-l.~~~ The effects of binding the [4Fe-4S]+ cluster of reconstituted biotin synthase to S-adenosyl-L-methionine were probed by examining the resonance Raman bands due to vFeS (320 - 340 ~ m - ' ) . ~ ~ ' FTIR evidence has been reported for the existence of gaseous FeF4,including a band at 758.5 cm-' assigned as v F ~ - F . ~ ~ ~ The IR spectrum of ~is-[Fe(BPM)~cl~], where BPM = bis(1-pyrazoly1)meth-

3: Vibrational Spectra of Transition Element Compounds

91

ane, includes vFeCl bands at 330 and 290 cm-', confirming the cis geometry.272 IR and Raman spectra of FeC13-doped poly(p-diethynylbenzene) showed that charge transfer led to the formation of FeC14- species, with characteristic wave number^.^^^ IR and Raman data were reported and assigned for the singlemolecule magnetic Fe8Br8and related species.274 Ab initio calculations of vibrational wavenumbers for Ru3were used to help in the assignment of earlier experimental data.275An IR band at 1936 cm-' for [RuH{ PPh(OEt)2}-(P(OEt),)},1+was assigned as ~ R u H Such . ~ ~modes ~ were also assigned for RuH2L2,where L = wide bite-angle diphosphines (2042 - 2075 ~ m - ' ) and ; ~ ~Cp*Ru(EPh3)H3, ~ where E = Sb or As (near 2000 ~ m - 9 . ~ ~ ~ Raman spectra of the oxidation products of methanol at Ru-Pt electrodes were consistent with the formation of M-CO species, with characteristic vRuC and vPtC bands.279 The resonance Raman spectrum (514 nm excitation) of [R~(biq)~(box)] +, where biq = 2,2-biquinoline, box = 2-(2-hydroxyphenyl)benzoxazole, includes vRuN(biq) at 372 cm-'.280 The complex C ~ R U ( P P ~ ~ )has ~ ( vRuN N ~ ) at 390 cm-l

281

Tran~-(RuCl(NO)(bpydip)]~+, where bpydip = N,N'-bis(7-methyl-2-pyridylmethylene)-l,3-di-iminopropene,gives an IR band due to vRu-NO at 497 cm-l .282 Skeletal mode assignments were proposed for IR bands from RuCl(qnh(N0). A normal coordinate analysis suggested extensive mixing of modes between vRu-NO and GRu-N-0. vRuCl was seen in the range 309 - 327 cm-l

283

gives vRuO at 486 The complex cis,cis,cis-RuC1~(DMSO-S)2(DMSO-O)(CO) cm-', vRuS at 421 cm-' and vRuCl376, 335 cm-'.284The Raman spectrum of Sr2Ru04was used to probe the nature of the superconducting spin-triplet st ate^.^*^ The complexes [{ (L)C1Ru1I}2(p-tppz)1Zf,where tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, L = a range of 2-arylazopyridines, all show a single vRuCl band (near 320 cm-'), showing equivalence of the two Ru-Cl bonds.286The cis-RuC12 arrangement in (28) is confirmed by the observation of two vRuCl bands in the

92

Spectroscopic Properties of Inorganic and Organometallic Compounds

Table 19 Skeletal assignmentsfor [OIOsN)zMC1J2- (jcm-') M =

Pd

Pt

vOsN voso vMCl

1072 900,887 342

1076 897,884 334

IR spectrum (315,223 ~ m - 9 The . ~ IR ~ spectrum ~ offac-RuC13(NC)(dppb),where dppb = 1,4-bis(diphenylphosphino)butane,includes vRuCl bands at 3 10 and 289 cm-1.288 The IR spectrum of trans-[Os(en)2(py)H](OTf)2contains a band assigned as vOsH at 2020 c111-l.~~~ IR spectra gave skeletal mode assignments for [(030sN)2MC12]2-,where M = Pd or Pt - Table 19.290 A mode at 302 cm-', assigned as vOsN, is seen in the resonance Raman The complexes spectrum of trans-(Cl)-[O~(bipy)(CO)(CH~CN)C12].~~' O~Cl~(NaiR)~,where NaiR = l-alkyl-2-(naphthyl)-(a/~)imidazoles, R = Me, Et, CH2Ph, all show vOsCl as two IR bands, i.e. cis-OsC12 geometry.292

Cobalt, Rhodium and Iridium

7

Earlier reference has been made to vibrational studies of C ~ ( a c a c )V ~C ; ~O~; ~ ~ CoBr2L2(where L = m-methylamine);'90and C o ( P ~ ) ( p y ) ~ . ~ ~ ~ Matrix-IR data for CoZ(C0) (from Co atoms + CO) include vCoCo 270.9 cm, GCo-C-0 357.9 cm-' and vCo-CO 488.7 cm-' (assignments backed by DFT calculations and isotopic shifts).293 Several Raman bands assignable as vCo-M, where M = Si, Sn or Pb, were seen for Ph3MCo(C0)4,i.e. vCo-Si 189 cm-l, vCo-Sn 171 cm-l, vCo-Pb 155

0

0

(29)

Skeletal (vMN, vMX) modes were assigned for metal(I1) halide bnzimidazole ( = benz) complexes, e.g. C ~ ( b e n zvCoN ) ~ 341 cm-'; C ~ ( b e n z ) ~ C vCoCl301,253 l~,

.295 Skeletal modes were also assigned from IR data for M(L), where M = Co, Ni or Pd; H2L = (29), including vM-N 520 cm-' (Co), 510 cm-' (Ni), 540 cm-' (Pd); v M - 0 380 cm-' (Co), 400 cm-' (Ni), 400 cm-' (Pd).296 The IR spectra of CO(NO~NCN)~(L)~, where L = pyrazole, imidazole and related, include two vCoN modes due to coupled Co-N(nitri1e) and Co-N(L) motions (280 - 306 ~ 1 1 1 - 9The . ~ ~IR ~ and Raman spectra of trans-[C0C12(trnd)~]l, where tmd = tetramethylethylenediamine, contain vCoN at 418 ~ m - ' . ~ ~ * Cm-l

3: Vibrational Spectra of Transition Element Compounds

93

The FTIR spectra of Li(A1xCol~x)02, where x = 0.1 - 0.5, show bands at 556 and 601 cm-', due to a2,, e, modes respectively.299Skeletal mode assignments, and normal coordinate analyses, were reported for MC142-, where M = Co or CLL3Oo

H (3 0)

The IR spectrum of (30) shows vRhH at 2036 ~ m - ' . ~ 'The ' first detailed study has been reported for HRh(C0)4,including vRhH at 2002.8 ~ m - ' . ~A' ~ band due to vRhC (e,) has been observed at 331 cm-' in the IR spectrum of [Rh(C0)4]+.303 DFT calculations have enabled skeletal mode assignments to be made from the IR and Raman spectra of t~ans-[RhF(C~H~)(P'Pr~)~l: vasRh-C2H4 5 14 cm-l, v,RhC2H4 471 cm-', vRhF 425 cm-', vRhP 349,306 cm-'. It appeared that vRhF and v,Rh-C2H4 were strongly Low-wavenumber Raman data were reported for M(q3-allyl)3,where M = Rh or Ir. These were assigned with the help of DFT calculations, and were consistent with a ground state of C1 symmetry.305 The IR spectra of M(Cp*)(Tp')Cl, where M = Rh or Ir, Tp' = unsubstituted or 3,5-Me2 disubstituted tris(pyrazolyl)borate, all contain vM-Cl bands in the range 260 - 280 ~ r n - ' . ~ ' ~ The complex [Ir(H)13(CO)2]-has vIrH at 2163 cm-1.307IR spectroscopy was used to observe vIrH for the new complex [I~(CNBU')~H](PF~)~.~'* The species (Et3P)3(H)21r = Si(H)(C6H3-Mes2-2,6) has vIrH at 2132 and 2079 ~ m - ' . ~ ' ~

8

Nickel, Palladium and Platinum

Earlier reference has been made to vibrational studies on the following: NdNi03;21NiCr204;'34M(L) (where M = Ni or Pd; H2L = N 2 0 2tetradentate l i g a n d ~ ) ? ~[(THF)C14Re=N-PdCl-(p-Cl)]22-;216; ~; [ O ~ O S N ) ~ M C ~(M ~]~ =- Pd, Pt);29"and the oxidation products of methanol at Pt/Ru electrodes.279 IR and Raman spectra have been reported, and skeletal modes assigned, for the spin-crossover complexes Fe(~y)~[M(cN)4] and F ~ ( ~ z ) [ M ( C N )where ~ ] , pz = pyrazine, M = Ni, Pd or Pt.310 vNiC modes were assigned from the IR and where M = Ni, Cu or Cd.311The Raman spectra of M(~iperidine)~Ni(CN)4, resonance Raman spectrum of the CO-adduct of [NiFe] hydrogenase from Desulfovibrio vulgaris contained vNi-Co at 375/393 cm-', and GNi-C-0 at 430 cm-l

312

IR spectra gave assignments to vNi-N3 and Ni-N(L) for [Nipy4(N3)]+and analogues containing substituted pyridine l i g a n d ~ .IR ~ ' ~and Raman spectra of M(mMA),12, where M = Ni, n = 4; M = Zn or Cd, n = 2, mMA = m-methylaniline,had vMN bands in the range 408 - 415 cm-', and vMI bands at

94

Spectroscopic Properties of Inorganic and Organometallic Compounds

206,177 cm-' (Ni), 201,159 cm-' (Zn), 209,180 cm-' (Cd).314 FTIR and Raman spectra of Ni(dmgh, where Hdmg = dimethylglyoxime, gave skeletal mode assignments, supported by DFT calculations. There was evidence for much mixing of modes, with vNiN (a,) contributing to Raman bands at 486 and 279 cm-', (b,) to IR bands at 429 and 270 ~ r n - ' . ~ IR, ' ~resonance Raman and SERS data were reported and assigned (with the help of ab initio calculations) for Ni(TAA), where TAA = dibenzo[b,i] [1,4,8,1l]tetraza[ 141annulene, e.g. vNiN 421 cm-' (a,) and 637 cm-' (b1,).316 Raman spectroscopy was used to characterise Mn-site-doped perovskite oxides, LaMnl-,NiXO3+d. Modes near 530 and 670 cm-' were dependent on nickelThe Raman spectra of thin films LiNi,Mn2.,04, where 0 < x < 0.5, include a band at 540 cm-' assigned as Y N ~ ~ " - OThe . ~ ' ~IR spectrum of ( N ~ ( ~ ~ z ) ( H ~ O ) ~ ] ( N O, ~ where ) ~ . ~pyz H ~=Opyrazine, ]~ has vNiO (of H20) at 487 c1~1-l.~'~ The resonance Raman spectrum of (PhTtBu)2Ni2(p-0)2, where PhTtBu = phenyltris((tert-butylthio)methyl)borate, gave assignments to Ni202 modes backed up by normal coordinate analysis and DFT calculations. v,NiO was seen at 590 cm-' (560 cm-' for "O), and 6,ONiO 184 ~ m - ' . ~ ~ ' The complex [HPd(dppeh]+ has vPdH at 1900cm-' in the IR Ab initio calculations have been carried out on the vibrational wavenumbers for M(CN)4X;- and M(CN)5X2,where M = Pd or Pt, X = F, Cl, Br or I.322 IR and Raman spectra of M(L)2C12, where M = Pd or Pt, L = 0-,rn- or p-dimethylphosphinylmethylene-oxyaniline (coordinated via the amino group), gave assignments to vMN near 540, 510 cm-' and vMCl near 350 and 340 cm-l

323

Skeletal mode assignments have been proposed (vMS, vMX) for [M(LH2)4]2+ and M(LH2)2X2,where M = Pd or Pt, LH2 = monothiomalonamide.324The complexes (31),where PR3 = PPh3, PEtPhz, PEt2Ph,PMePh2, all show vPd-Cl in the range 285 - 297 The IR spectra of MC12[(C4H3S)3A~]2, where M = Pd, Pt, have vMCl at 328 cm-l (Pd) or at 279 and 328 cm-' (Pt).326 The complex ~is-PdCl~(L~'~yl)~, where La'lyl = (32), has vPdCl IR bands at 402.7 and 386.5 cm-' cm-', confirming cis geometry.327Ab initio and DFT calculations gave predicted vibrational wavenumbers for MX2- and M2X:-, where M = Pd(I1) or Pt(II), X = Cl, Br or I.328

The IR spectra of (33), where S-N = (34) (R = Me or 'Bu) include vPt-CH3 (trans to S) 565 cm-', vPt-CH3 (trans to N) 510 cm-' and Y P ~ - ( C H(ax) ~ ) ~480 469. c111-l.~~~ The resonance Raman spectrum of (~PT-DAB)P~(CH~)~, where

3: Vibrational Spectra of Transition Element Compounds

95 Me

/

CJHc)O

(35)

'Pr-DAB = N,N'-di-isopropyl-l,4-diazabutadiene, contains coupled vPtC/vPtN bands at 599,575,564 c111-l.~~~ Skeletal (vPtN, vPtO) assignments were made from the IR spectra of cisPt(L)2X,where L = heptamethyleneimine, X = cyclobutane dicarboxylate and other d i c a r b ~ x y l a t e sThe . ~ ~ ~IR spectrum of (35) includes vPtP 457 cm-', vPtCl 326 IR and Raman spectra gave detailed assignments and normal coordinate analyses for a range of platinum oxalato ( = ox) complexes: [Pt11(SCN)2(ox)]2-, [Pt"( SCN),(OX)]~-;~~~ [PtIVX4( ox)]'- (X = C1 or Br);334trans- [Pt"F2( ox)2I2-, [Pt1vF4(o~)]2-;335 and ~is-[Pt'~X2(0~)2]~(X = C1, Br or I).336 High-pressure IR and Raman spectra of ~is-(Ph3P)2Pt(SH)~ show that the vPtS wavenumber is strongly pre~sure-dependent.~~~ The complex anion [PtF4I2- has v,,PtF at 515 cm-', and deformation modes at 255 and 230 cm-' in the IR spectrum, with v,PtF at 595 and 565 cm-' in the Raman Resonance Raman data (v,XPtX) were used to probe the multiphonon excitations in [Pt(en)2X2][Pt(en)2]-(C104)4.339

9

Copper, Silver and Gold

Earlier reference has been made to vibrational studies on the following: C ~ C U ~ TL ~~ ~COU~ , ~M; ~ haem-a3-C=N-CuB ~ - ~ ~ ~ ; ~ complex ~ ~ of oxidised cytochrome aa3 ~ x i d a s e ;Cu(benzhX2 ~~~ (benz = benzimidazole, X = C1, Br);295 C U C ~ ~C ~ - (;p~i p~) ~ N i ( C N )and ~ ; ~{'PW9V3040[Ag(bipy)]2-[Ag2(bipy)3]2} l .Io5 The resonance Raman spectrum of [(ArC02)2C~2(THF)2] +,where Ar = 2,6dimesitylbenzene, includes a strong band at 244 cm-', due to a mode with considerable vCuCu character.340For the side-on p,q2:q2-bridgedCu2(S2)complex [ C U ~ ' ( H B ( ~ , ~ - ' P ~ ~ ~ Z the ) ~resonance } ] ~ ( S ~ ) ,Raman band at 260 cm-' was assigned as vCuCu (ag),with that at 495 cm-' as vCuS (b1J (for 32S- shifting to

96

Spectroscopic Properties of Inorganic and Organometallic Compounds

483 cm-' for 34S).341 IR and Raman spectra of C U ( C M A ) ~ ( H Iwhere ~ ) ~ , HIm = imidazole, CMA = 9,10-dihydro-9-oxo-1O-acridine acetate ion, have v,,CuN at 269 cm-', v,CuN at 244 crn-l, va,CuO at 337 cm-' and v,CuO at 300 c111-l.~~~ Skeletal mode assignments from the resonance Raman spectra of [{(R-TMPA)CU")~(O~)]~+, where R = H, M e 0 or Me2N,are summarised in Table 20.343 gives IR bands due to vCuN The polymeric cation [C~(4,4'-bipy)2(HzO)?+]~ at 393 and 337 cm-' and v C u 0 at 454 ~ m - ' .The ~ ~ IR spectra of [[CU(GLYO)~.,(OX),(~~~~)]~.~H~O},, where GLYO = glyoxalate anion, ox = oxalate, have vCuN at 266/234 cm-' (x = 0.56) or 243 cm-' (x = 0.71), with YCUOat 339 cm-' in both cases.345Skeletal mode assignments for Cu(L)C12, CU(L)~+ and C U ( L ) ( P P ~ ~ ) where ~ C I , L = (36), included vCuN near 460 cm-', vCuP2 159 cm-', vCuS near 350 cm-', and vCuCl 237 - 271 ~ m - ' . ~ ~ ~ S k e l e t a l mode assignments were also proposed from the IR spectra of Cu,(L1)(L2)nXn, where n = 1 or 2, L1 = 4,6-diacetylresorcinol, o-hydroxybenzaldehyde or ohydroxyacetophenone; L2 = bipy, phen or Me4en.347

Far-IR RAIRS data from a range of oxygen-containing organic molecules adsorbed on Cu(ll0) or Cu(100) included features due to vCu0 modes. Thus, diketones gave a band near 300 cm-' due to the vCu-0 = C unit of a delocalised keto-enol chelate.348vCu0, vCuCl and GCuCl modes were assigned from the Raman spectra of the basic copper chloride minerals atacamite and parata~amite.~~~ Resonance Raman spectra gave characteristic bands for the [Cu2(P-O)~]~+ core from intermediates in the oxidation of LCu(MeCN)complexes, where L- = range of P-diketiminate anions.35o The Raman spectrum of [C~2(btec)(H20)4.2H20]~, where H4btec = 1,2,4,5-CsHz(COOH)4has YCUOat 305 Raman data for Rul-,A1,Sr2GdCu2Osshow that the feature at 150 cm-I (Cu vibration along the c-axis) is almost independent of x (= 0, 0.05, 0.10, 0.15).352 The Raman spectrum of Bil,95Pb~.02Sr2,47Cal,9Cu30~ film has two characteristic Table 20 Skeletal assignmentsfor [((R-TMPA)CU")~(O~)]~+ (lcm-') R=

YCUO

YCUN,,

H Me0

561 (I6O2),535 ("02) 557 ( 1 6 0 2 ) , 533 (I8O2)(symm) 525 ( 1 6 0 2 ) , 506 (I8O2)(as)

429 427

Me2N

557 (1602), 491 ( 1 8 0 2 )

426

3: Vibrational Spectra of Transition Element Compounds

97

bands at 632 and 674 ~ r n - ' . ~ ~ ~ The Raman spectra of copper-rich CuGaS2thin films contain a characteristic feature at 472 cm-'.354Resonance Raman spectra gave assignments to vCuS for the blue copper sites in wild-type stellacyanin (386 cm-') and its Q99M (393 cm-') and Q99L (417 cm-') axial mutants. Thus reducing the donor strength of the axial ligand increases the strength of the Cu-S bond.355 Resonance Raman data have also been reported for C~(L)[HB(3,5-~Pr~pz)~l, where L = SMeIm (five-coordinate,YCUS218 cm-') or SCPh3(four-coordinate, vCuS 431 cm-'). These show the marked influence of coordination geometry on Y C U S .For ~ ~ [(TMPA)CU-S-S-CU(TMPA)]~+ ~ (the first copper complex with an end-on bridging disulfide ligand) v,CuS gives a resonance Raman band at 316 cm-l, with v,,CuS in the IR at 478 cm-'. Both bands showed expected sulfur isotopic shifts.357 Ab initio calculations have been reported for the vibrational wavenumbers of CUnCln clusters, where n = 1 - 4.358IR and Raman spectra of the CuC12- anion in the vCuCl region have been reported and assigned for a number of aminoguanidinium and related salts.359 Skeletal (vCuX) modes were assigned from the IR and Raman spectra of CuXE2,where X = Cl, Br or I, E = Te; X = Cl or Br, E = Se.360The IR spectra of CuX(PCy3)2gave the following assignments to vCuX: 265 cm-' (Cl), 192 cm-I (Br) and 156 cm-' (I).361 Ab initio calculations have been made of vAgN wavenumbers for pyridine adsorbed on a silver surface (calculations on an Ag4+ model gave the best agreement with experiment).362The Raman spectrum of AgI-HSA (= human serum albumin) shows bands at 224 cm-' and 246 cm-' due to vAgN and ~ A g s . IR 3 ~and ~ Raman spectra of polymeric {Ag(L)),, where L- = 1-methyluracilate, include vNAgN at 450, 362 cm-' and vAgO in the range 250 - 280 cm-l

364

SERS data for 4'-(5-mercaptopentyl)-2,2':6',2"-terpyridinyl on a silver electrode surface showed a vAgS band at 310 cm-', i.e. coordination has occurred via the S atom.365 The gas-phase IR spectrum of AgI shows a major band at 192 cm-' due to v of the monomer, with a weaker feature at 205 cm-' due to vasof the AgJ3 t ~ - i m e r . ~ ~ ~ A detailed study of AuF in its X12+ground state shows that We = 563.697(32) cm-' and Wexe = 3.27235(76) cm-1.367Vibrational modes were calculated by Hartree-Fock methods for AuF6- -in good agreement with experimental data.368 IR bands due to vAuCl were assigned for complexes (37) (321 cm-')369and (38) (326 CM-').~~'

Spectroscopic Properties of Inorganic and Organometallic Compounds

98

10

Zinc, Cadmium and Mercury

Earlier reference has been made to vibrational studies on Zn,Mgl-,Fe2.,Nd,04;20 the Bi203-Zn0-Nb205system;118ZnMn20$07 M(mMA)212(M = Zn, Cd, mMA = m-methylaniline);314C d ( b e n ~ ) ~(benz X ~ = benzimidazole, X = C1 or Br);295 and Cd(~ip)2Ni(CN)~.~*~ Skeletal (YMN,YMS)modes were assigned from the IR and Raman spectra of Zn(ISTSC)2 and Hg(ISTSCH)Br2, where ISTSCH = isatin-2-thiosemicarb a ~ o n eIR . ~and ~ ~Raman data for [MBr2(mMA)Jn, where M = Zn (n = l), CD or Hg (both n = a), mMa = rn-methylaniline, gave the assignments listed in Table 21.372 Raman spectra of unannealed ZnO films include an asymmetrical band at 570 cm-l .373 Raman spectroscopy was used to characterise the structure of ZnO film produced by plasma-assisted MOCVD. The film was found to be virtually free of strain (compared to ZnO Raman imaging was used to probe the pressure-induced phase transitions for ZnSe near 5 and 34 GPa.375The Raman spectra of ZnSe nanorods gave bands at 257 and 213 cm-' due to longitudinal and transverse optical phonons respectiveiY.376 Variable-temperature Raman spectra (- 196 - 8OOOC) of glassy, supercooled and molten ZnC12 and ZnBr2 gave evidence on temperature-induced structural changes.377Similar experiments were reported for glasses xZnC12.(1x)A1CI3,where x = 1,0.9,0.8,0.6,0.4,0.2,0.1, 0.378 The Raman spectra of glasses xSb203.(1-x)ZnC12, where x = 0.25, 0.50 or 0.75, gave evidence for the species [Zn(ClZn)2(OSb)2].379 Variable-temperature Raman spectroscopy (60 - 295 IS) found no evidence for thermal phase t a n s f o r m a t i o n ~ . ~ ~ ~ IR and Raman spectra of CdX,(bpytm), where bpytm = bis(2-pyridylthio)methane, X = Br or I, gave the following assignments: vCdBr 192,179 cm-' (IR), 175 cm-' (Raman); vCdI 162,151 cm-' (IR), 147 cm-' (Raman).38' The Raman spectrum of Hg2[B(CN)4]2contains a band due to vHgHg at 173 c 1 ~ 1 - l .An ~ ~equivalent ~ band was seen at 177 cm-' in the Raman spectrum of Hg2(CH3S03)2.383 Ab initio calculations have been made of vibrational wavenumSkeletal assignments for [MBr2(mMA)2], (lcm-') Table 21

+

M = vM-N vM-Br(br) vM-Br(t)

Zn 416,386 226,205

Cd 350 183,154 214

Hg 376,361 186 247

3: Vibrational Spectra of Transition Element Compounds

Table 22

99

Skeletal assignments for [ H s ( N H ~ ) ~ ] ' +(lcm-')

bers for HgCH3 and HgCH3+.3s4 Skeletal mode assignments are given in Table 22 for [Hg(NH3)4]2+,as the C104The Raman spectrum of cinnabar, HgS, includes vHgS modes at 353,342,290, 277 and 253 c111-l.~~~ Bands were assigned to vHgX modes from the IR spectra of Hg(Ham4DM)X2, where Ham4DM = 2-pyridine formamide N(4)-dimethylthiosemicarbazone, X = C1 (208 cm-'), Br (166 cm-') or I (147 cm-'). vHgN(imine) bands were seen at 448 cm-' (Cl), 422 cm-' (Br) and 417 cm-' (I), with vHgS 240 - 250 cm-' cm-' in all cases.387Raman spectroscopy was used to study phase transitions between yellow polymorphs of Hg12.388

11

Actinides

Earlier reference has been made to vibrational studies of [(UO2)2(V0)2(106)201'- ;78 [U02(Cr04)(I03)2]2';"' and Th(N3)4.28 IR and Raman data were reported for Na2ThF6,and assigned using factor analysis. They were consistent with the presence of trigonal tricapped systems.389 The matrix-IR spectrum of U(BH4)4,i.e. U[(p-H)3BHI4,included a band at 481 cm-' assigned as vU-B (t2).390Uranium atoms and CO react to give matrixtrapped CUO (as CUO.Ar, clusters) with IR bands at 852.5 and 804.3 cm-' (l2C1Q values).391 Changes in v1 (v,U02) of U022+in calcium nitrate hydrate melts were used to probe structural interactions.392The Raman spectra of M02(103)2(H20),where M = U, Np or Pu, gave the following assignments to vsM02: 881 cm-' (U), 872 cm-I (Np), 856 cm-' ( P u ) .Numerous ~~~ other studies were made of IR and/or Raman spectra of U 0 2 2+-containing Raman spectroscopy was used to follow the phase behaviour of Cm-Zr oxide phases. A band at 283 cm-' was assigned to 60-Cm-0!06

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341. P. Chen, K. Fujisawa, M. E. Helton, K. D. Karlin and E. I. Solomon, J . Am. Chem. SOC.,2003,125,6394. 342. D. Dobrzynska, M. Duczmal, J. Jezierska and L. B. Jerzykiewicz,Polyhedron, 2002, 21,2381. 343. M. J. Henson, M. A. Vance, C. X. Zhang, H.-C. Liang, K. D. Karlin and E. I. Solomon, J . Am. Chem. SOC.,2003,125,5186. 344. P. A. M. Williams, E. G. Ferrer, E. J. Baran, 0. E. Piro and E. E. Castellano, 2. anorg. allg. Chem., 2002,628,2044. 345. A. Castiiieiras, S. Balboa, R. Carballo and J. Niclos, 2.anorg. allg. Chem., 2002,628, 2353. 346. M. Ghassemzadeh, F. Adhami, M. M. Herani, A. Taeb, S. Chitsaz and B. Neumiiller, Z . anorg. allg. Chem., 2002,628,2887. 347. A. Taha, Spectrochim. Acta, 2003,59A, 161 1. 348. V. Humblot, C. J. A. Bingham, D. le ROUX,M. E. Mateo, A. McNutt, T. S. Nunney, L. M. Ortega, A. J. Roberts, J. Williams, M. Surman and R. Raval, Surf Sci, 2003, 537,258. 349. R. L. Frost, W. Martens, J. T. Kloprogge and P. A. Williams, J . Raman Spectrosc., 2002,33,801. 350. D. J. E. Spencer, A. M. Reynolds, P. L. Holland, B. A. Jazdewski, C. Duboc-Toia,'L. Le Pape, S. Yokota, Y. Tachi, S. Itoh and W. B. Tolman, Inorg. Chem., 2002,41, 6307. 351. R. Cao, Q. Shi, M. Hong, W. Bi and Y. Zhao, Inorg. Chem., 2002,41,6161. 352. D. C. Ling, S. G. Yang, S. C. Hsu and H. L. Liu, J . Low-Temp. Phys., 2003,131,659. 353. C. Mejia-Garcia, E. Diaz-Valdes, G. Contreras-Fuente, J. L. Lopez-Lopez and M. Jergel, Thin Solid Films, 2002,414, 123. 354. M. S. Branch, P. R. Berndt, J. R. Botha, A. W. R. Leitch and J. Weber, Thin Solid Films, 2003,431-2,94. 355. S . D. George, L. Basumallick, R. K. Szilagyi, D. W. Randall, M. G. Hill, A. M. Nerissian, J. S. Valentine, B. Hedman, K. 0. Hodgson and E. I. Solomon, J . Am. Chem. SOC.,2003,125,11314. 356. L. Basumallick, S. George, D. W. Randall, B. Hedman, K. 0.Hodgson, K. Fujisawa and E. I. Solomon, Inorg. Chim. Acta, 2002,337,357. 357. M. E. Helton, P. Chen, P. P. Paul, Z. Tyeklar, R. D. Sommer, L. N. Zakarov, A. L. Rheingold, E. I. Solomon and K. D. Karlin, J . Am. Chem. SOC.,2003,125, 1160. 358. M. Hargittai, P. Schwerdtfeger, B. Rkffy and R. Brown, Chem. Eur. J., 2003,9,327. 359. L. A. Sheludyakova and T. V. Basova, J . Struct. Chem., 2002,43,581. 360. T. Nilges, S. Zimmerer, D. Kurowski and A. Pfitzner, 2. anorg. allg. Chem., 2002, 628,2809. 361. G. A. Bowmaker, S. E. Boyd, J. V. Hanna, R. D. Hart, P. C. Healy, B. W. Skelton and A. H. White, J . Chem. SOC.,Dalton Trans., 2002,2722. 362. A. Vivoni, R. L. Birke, R. Foucault and J. R. Lombardi, J . Phys. Chem.,B, 2003,107, 5547. 363. X.-C. Shen, H. Liang, J.-H. Guo, C. Song, X.-W. He and Y.-Z. Yuan, J . Inorg. Biochem., 2003,95,124. 364. B. Morzyk-Ociepa and D. Michalska, Spectrochim. Acta, 2003,59A, 1247. 365. A. C. Sant'Ana, W. A. Alves, R. H. A. Santos, A. M. D. Ferreira and L. A. Temperini, Polyhedron, 2003,22, 1673. 366. A. Kovacs and R. J. M. Konings, J . Mol. Struct., 2002,643,155. 367. T. Okabayushi, Y. Nakaoka, E. Yamazaki and M. Tanimoto, Chem. Phys. Lett., 2002,366,406.

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Spectroscopic Properties of Inorganic and Organometallic Compounds

368. J. F. Lehmann and G. J. Schrobilgen, J . Fluorine Chem., 2003,119,109. 369. J. Vicente, M. T. Chicote, M. D. Abrisqueta and M. M. Alvarez-Falcon, J . Organometal. Chem., 2002,663,321. 370. 0.Crespo, E. J. Fernandez, P. G. Jones, A. Laguna, J. M. Lopez-de Luzuriaga, M. Monge, M. E. Olmos and J. Pkrez, J. Chem. Soc., Dalton Trans., 2003,1076. 371. N. T. Akinchan, P. M. Droidiewski and W. Holzer, J . Mol. Struct., 2002,641,17. 372. K. Golcuk, A. Altun and M. Kumru, Spectrochim. Actu, 2003,59A, 1841. 373. C. Roy, S. Byrne, E. McGlynn, J.-P. Mosnier, E. de Posada, D. O’Mahony, J. G. Lunney, M. 0.Henry, B. Ryan and A. A. Cafolla, Thin Solid Films, 2003,436,273. 374. X. Wang, S. Yang, J. Wang, M. Li, X. Jiang, G. Du, X. Liu and R. P. H. Chang, Opt. Quantum Electronics, 2002’34, 883. 375. P. Colomban and M. Havel, J . Raman Spectrosc., 2002,33,789. 376. P. V. Teredesai, F. L. Deepak, A. Govindaraj, A. K. Sood and C. N. R. Rao, J . Nanosci. Nunotech., 2002,2,295. 377 S. N. Yannopoulos, A. G. Kalampounias, A. Chrissanthopoulos and G. N. Papatheodorou, J . Chem. Phys., 2003,118,3197. 378. A. G. Kalampounias and S. N. Yannopoulos, J . Non-Cryst. Solids, 2003,326-7,109. 379. J. A. Johnson, D. Holland, J. Bland, C. E. Johnson and M. F. Thomas, J . Phys. : Condens. Matter, 2003,15,755. 380. R. L. Carter, Spectrochim. Acta, 2002,58A, 3185. 381. A. Amoedo-Portela, R. Carballo, J. S. Casas, E. Garcia-Martinez, A. SanchezGonzalez, J. Sordo and E. M. Vazquez-Lopez, Polyhedron, 2003,22,1077. 382. M. Berkei, E. Bernhardt, M. Schiirmann, M. Mehring and H. Willner, Z . anorg. allg. Chem., 2002,628, 1734. 383. M. S . Wickleder, 2. anorg. allg. Chem., 2002,628, 1848. 384. E. P. F. Lee and T. G. Wright, Chem. Phys. Lett., 2003,376,418. 385. P. Nockemann and G. Meyer, 2. anorg. allg. Chem., 2003,629,123. 386. R. L. Frost, W. N. Martens and J. T. Kloprogge, Neu. Jahrb. Mineral., Monatsh., 2002,469. 387. E. Bermejo, A. Castiiieiras, I. Garcia and D. X. West, Polyhedron, 2003,22, 1147. 388. M. Hostetler, H. Birkedal and D. Schwarzenbach, Helu. Chim. Acta, 2003,86,1410. 389. E. Teixeira, J. Mendes-Filho, P. E. A. Melo, A. P. Ayala, J. Y. Gesland, C. W. A. Paschoal and R. L. Moreira, Vib. Spectrosc., 2003,31, 159. 390. A. Haaland, D. J. Shorokhov, A. V. Tutukin, H. V. Volden, 0. Swang, G. S. McGrady, N. Kaltsoyannis, A. J. Downs, C. Y. Tang and J. F. C. Turner, Inorg. Chem., 2002,41,6646. 391. L. Andrews, B. Liang, J. Li and B. E. Bursten, J . Am. Chem. Soc., 2003,125,3126. 392. T. Fujii, H. Yamana and H. Moriyama, J . Nucl. Sci. Technol., 2002, Suppl. 3, 336. 393. A. C. Bean, B. L. Scott, T. E. Albrecht-Schmitt and W. Runde, Inorg. Chem., 2003, 42, 5632. 394. P. M. Almond and T. E. Albrecht-Schmitt, Inorg. Chem., 2002,41,5495. 395. S. N. Tripathi and P. N. Namboodiri, Powder Dig, 2003,18,42. 396. K. Mizuoka and Y. Ikeda, Inorg. Chem., 2003,42,3396. 397. K. Mizuoka, S.-Y. Kim, M. Hasegawa, T. Hoshi, G. Uchiyama and Y. Ikeda, Inorg. Chem., 2003,42,1031. 398. A. J. Norquist, M. B. Doran, P. M. Thomas and D. O’Hare, J . Chem. Soc., Dalton Trans., 2003,1168. 399. K. C. S. de Almeida, T. S. Martins, P. C. Isolani, G. Vicentini and J. ZukermanSchpector, J . Solid State Chem., 2003,171,230. 400. T. R. Varga, A. C. Benyei, Z. Fazekas, H. Tomiyasu and Y. Ikeda, Inorg. Chim. Acta,

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2003,342,291. 401. U. Casellato, S. Tamburini, P. Tomasin and P. A. Vigato, Inorg. Chim. Acta, 2002, 341, 118. 402. P. Ondrus, R. Skala, F. Veselovsky, J. Sejkora and C . Vitti, Amer. Mineral., 2003,88, 686. 403. T. Soga, J. Nucl. Sci. Technol.,2002, Suppl. 3,433. 404. G. le Saout, P. Simon, F. Fayon, A. Blin and Y. Vaills, J . Raman Spectrosc., 2002,33, 740. 405. Y. Oda and A. Aoshima, J . Nucl. Sci. Technol., 2002,39,647. 406. Z. Assefa, R. G. Haire and P. E. Raison, J . Nucl. Sci. Technol.,2002, Suppl. 3, 82.

4 Vibrational Spectra of Some Co-ordinated Ligands BY G.DAVIDSON

1

Carbon, Silicon and Tin Donors

Laser-ablated titanium atoms react with C2H2/02 mixtures to give OTi(0H)CCH trapped in an argon matrix. The IR spectrum of this has YCC at 1972.2cm-' (1904.0 cm-' for I3C),with YOHat 3703.5 cm-' (YOD2731.5 cm-').I The complex (1) gives an IR band due to YC= C at 1628 cm-'.* For (2), YC=Cof the coordinated alkyne contributes to IR features at 1640,1598 and 1562 cm-1.3

The IR spectra of (3), X = Ni[P(OPh)3], [Ti] = (q5-CsH&Me3)2Ti, and related species, show YC& in the range 1790 - 1870 c1~1-l.~ For (3), X = Pd-PPh3,YC=Cis at 1816 ~ m - ' while , ~ for X = Cu(9-CI4Hg)this mode is at 1860 Spectroscopic Properties of Inorganic and Organometallic Compounds, Volume 37 0The Royal Society of Chemistry, 2005 114

4: Vibrational Spectra of Some Co-ordinated Ligands

Table 1 HCrCCH Cr(C*Hd

115

Ligand mode assignmentsfor Cr -k C2Hz reaction products (fcm-') YCC GCCH GCCH YCC GCCH (out-of-plane)

1955.2 638.4 635.5 1476.4 991.9

cm-'. This final figure reveals strong o-donation from the organic ligand on the copper.6The complexes (4) have v C 0 at very low values (1870 cm-' for M = Ti, 1879 cm-' for M =V), showing strong electron donation from the cyclo-octadienyl ligands to M.7 IR and Raman spectra were analysed to give assignments to cyclopentadienyl ligand modes for Cp2Zr(OSiFc2)20 and [Cp2Zr(OSiFc2)O12,where Fc =ferrocenyl.8 Argon-matrix IR data were reported for the reaction products of laser-ablated chromium atoms with C2H2.Evidence was found for HCrCCH and Cr(C2H2)Table l.9 DFT calculations of vibrational wavenumbers for ($-naphtha1ene)chromiumtricarbonyl gave good agreement with experiment." The complexes (9,where M = Mo or W, R = Me or Ph, all have a ketonic vC = 0 mode in the range 1676- 1680 cm-lin their IR spectra." The IR spectra (vC0) of CF3COO(L-L)(C0)2M=C-C=CR, where M = Mo or W, L = L = bipy or 4,4'-Me2-Bipy,R = SiMe3,Ph, p-to1 or t-Bu, in solution are consistent with the formation of dimers and oligomers.12The complex (6) gives two IR bands due to coordinated alkynes, at 1588 and 1565 cm-', showing strong Mo-alkyne binding.13 where R = Et, 'Pr, The complexes [W(CO)(NCR)(P(OiPr)3)z(r2MeC2Me)]+, 'Bu, Ph or CH2Ph,all have IR bands from vCC of the q2-alkynenear 1580 cm-'. The band due to vCN of CNR decreases from 2285 cm-' (R = Et) to 2252 cm-' (R = CH2Ph).14The IR spectra of W12(CO)(NCR)(q2-HC2Bu'), where R = Me, Et, 'Pr, 'Bu or Ph, include vCC bands near 1710 and 1690 cm-' from the two q2-alkyne ligands.15The low formal oxidation state of the tungsten in (7) produced low values for both v C 0 (1860 cm-') and vNO (1450 crn-').l6 The IR spectrum of WCl(SnC13)(CO)3(NCMe)(PPh3) includes vSnCl from the SnC13ligand at 330 cm-'.17 The IR spectra of matrix-isolated R3Re02, where R = CH3, CHD2, CD3, all gave ligand mode assignments, which were supported by DFT calculations.18 Similar data for (CH3)4Re= 0 and its dl2-analogue yielded the following assignments: vCH (al) 2975.4, 2887.4 cm-' (2238.6, 2109.5 cm-' for D), 6CH3 (al) 1419.4, 1231.3 cm-' (1055.0, 937.9 cm-l for D). For the related D2C = Re(0)(CD3)3,vCD2 bands were seen at 2212.3 and 2134.1 crn-'.l9 Detailed assignments were also proposed from IR spectra of matrix-isolated C2H5Re03 and C2D5Re03.20 The complex (8) and related species show v C = O near 1556 cm-1.2' The vinylidene grouping in (9) gives an IR band due to vC = C at 1649 cm-'.22 TRIR measurements (vC=C) were used to characterise an excited triplet state for fac-[Re1(phen)(C0>2(trans-bpe)]+, where bpe = 1,2-bis(4-pyridyl)ethane.2'

116

Spectroscopic Properties of Inorganic and Organometallic Compounds 0

0

/

W-

ON

-C-CMe3

C=

02 (7)

IR (YCH)data for [Ni(C2H2)J+,where n = 3 - 6, (formed by laser vaporisation in a pulsed nozzle source) gave shifts consistent with the formation of metal cation ~c-complexes.~~

4: Vibrational Spectra of Some Co-ordinated Ligands

117

The acyl ligand in (10)showed an IR band due to YC= 0 at 1688 .25 Both of the complexes (ll), where R3 = Ph3 or EtPh2, gave two Y C = O bands from the formyl groups, e.g. for the PPh3 complex, 1732, 1681 cm-1.26Laser-ablated Pd atoms react with C2H2/Arto form matrix-trapped Pd(q2-C2H2)(YCC1566 cm-I) and Pd(q2-C2H2)2(YaSCC) 1765 cm-'.27 PEt,

PEt3

Ph-Pt

I I

-

L

-

I I PEtq

Pt -Ph

t

'Ph

The complex (12), where L = -C&-, has YC=Cat 2087 cm-', while for L = SiPh2,this band is at 2027 cm-'.28 For L = (13) and related units, YCECis in the , ~ ~ for L = 1-(2-ethylhexyloxy)-4-methoxybenzenerange 208 1 - 2087 ~ m - ' while 2,5-diyl, it is at 2095 cm-l.MThe IR spectra of (14), where €3 = tBu, SiMe3, Ph, Tol, C6H4CF3-4,CSH4N-2or C ~ H ~ C G Call H , include two strong vC=C bands . ~ ~ (15), vC=C is at 2075 (2008 - 2108 cm-') due to the cis-alkynyl l i g a n d ~ For cm - 1 .32 The IR spectrum of trans-PtC12(q2-C2H4)(H2ten), where H2ten = 4-hy1,ldroxy-2-met hyl-N-2-pyridyl-2H-t hieno[2,3-e]- 1,2-thiazine-3-carboxamidedioxide, has a band at 1524 cm-', due to YCCof the coordinated ethene.33 The complex TpFe(CO)(PMe3)(COMe),where Tp = hydrotris(pyrazoly1)borate, has an IR band due to YC= 0 of the acetyl ligand at 1586 ~ m - ' The . ~ ~TR spectra of the bridging carbyne complexes (p-EtOC)(p,-RSe)Fe2(C0)6, where R = p-Me-, rn-Me-, o-MeC6H4and related, include YC-O-Ccarbyne in the range 1290 -1300 ~ r n - ' . ~IR ' data for (16) include YNH at 3334 cm-' and Y C = N at 1567 cm11.36The related species (17),where R = H, Me, M e 0 or C1, have YC= C 1595 - 1598 cm-', Y C = N 1560 - 1570 cm-' and YNH 3310 - 3270 ~ m - ' . ~ ~ IR bands due to YC= O(dione) were observed at 1745 and 1715 cm-' in the IR The complex (19), where spectrum of HR~~(CO)~(bpcd)(p3-q~,q~,q'-C=CPh).~~

Spectroscopic Properties of Inorganic and Organometallic Compounds

118

H

(1 X’I

f P Cl-Ru-

0 r2 I

A ph211 Cl----KU

‘=c=(

(23)

I Fe

[Ru2] is a diruthenium unit bridged by substituted aminopyridines, has YC=C bands in the IR spectrum due to free (2152 cm-’) and complexed (2048 cm-’) alkynyl groups.39(20) shows vC=C at 2001 cm-’ and YC= 0 at 1603 cm-I in its IR spectrum?0 The resonance Raman spectrum of (21) includes YCCC at about 1960 cm-’, and is consistent with d(Ru)+z*(CCC) MLCT character for the electronic tran~ition.~’ The complexes (22) show IR bands due to vC=C near 2030 cm-’

4: Vibrational Spectra of Some Co-ordinated Ligands

119

(free) and 1985 cm-' (complexed), together with Y=CH at 3284 cm-' in both cases."2 For (23), where Tp = H B ( ~ z ) ~a- ,characteristic v C = C = C IR band is seen at 1946 ~ m - ' .The ~ ~IR spectrum of q2-Cho[Ru(NO)(PPh3)I2shows typical bands for the q2-C60coordinated to ruthenium atoms via o-n intera~tions.4~ The novel complexes C p R ~ ( P p h ~ ) ~ ( S nwhere x ~ ) , X = F, C1 or Br, give IR bands from the coordinated SnX3- units at 490 cm-' (X = F), 272,290 cm-I (Cl) or 260,265 cm-I (Br).45

H

I

(24)

The IR bands due to YC= 0 of the substituted maleic anhydride ligand in (24) are at 1798 and 1724 cm-'. The decreases by comparison with the free ligand values were consistent with coordination of the C = C bond to Co as shown.46 Adsorption of crotonaldehyde to a Rh/Ti02 catalyst produced an IR band at 1660 cm-' due to coordination of C = 0 to the rhodium atom.47An IR band is seen at 1730 cm-' due to Y C = O for [Rh(L)(COMe)I]+, where L = 2,6bis(benzy1thiomethyl)pyridine:' An in situ FTIR study of the rhodium-catalysed hydroformylation of 1-octene characterised the intermediate C8HI7C(O)Rh(CO)4 (vC=O, YC= 0),suggesting that this species is trigonal bipyramidal, with an axial acyl ligand.49The IR spectrum of (25) has vSiH at 2030 cm-'.50 RAIRS data were used to identify surface bound CF3 and CF2 units following CF31adsorption on Cu( 1 Laser-ablated copper atoms react with C2H2and C2H2/CO mixtures to form Cu(C2H2)2and Cu(CO)(C2H2),for which some assignments are summarised in Table 2.52There is IR evidence for the formation of two Cu-C2H2species by adsorption of ethyne on vacuum-dehydrated CuNaY zeolite, i.e. vCC near 1832 and 1814- 1812 cm-'; Y,CH 3271 and 3251 cm-'; v,,CH 3202

Table 2

Ligand mode assignments for Cu products (/cm-*)

CU(C2H2)2

vascc

Cu(ClH,)(CO)

vCO vcc

1658.9 1622.1 1604.5 2039.9 1644.2

+ C2H2 or C2HZ/C0 reaction

(all I2C) (l2C2H2/I3C2H2) (all 13C) (1994.6 for 3CO) (1589.3 for 13C2H2)

120

Spectroscopic Properties of Inorganic and Organometallic Compounds

and 3174 ~ m - ' . ~ ~ ~ ~ - KE~= - PS,) ~Se, or Te, The complexes ( M ~ & E - C U ) ~ ( ~ P ~ ~ P C = C P Pwhere have Raman bands due to YC=C as follows: 2122 cm-' (S), 2117 cm-' (Se) and 2116 cm-' (Te).54Adsorption of C2H4on a CuNaY zeolite gives IR bands due to YCH(near 3011 cm-'), YCC(1545/1535 cm-') and 6,CH2(1278/1264 cm-') from a (q2-C2H4)Cuunit.55DFT calculations of vibrational wavenumbers for C2H4 adsorbed on Cu(110)and Ag( 110)show that n and n* interactions are important for Cu, but that n* interactions are negligible for Ag.56 A vibrational spectroscopic study of propene on oxygen-modified Ag(ll1) gave evidence for a gradual transition from n-bonded to di-o-bonded propene as the percentage of oxygen adatoms in~reased.~'

The IR spectrum of (26) included YC=C (free) at 2214 cm-', and vC=C (complexed)2094 ~ m - ' . ~ The * coordinated alkyne groups in (27) gave IR absorption at 21 30 cm-'.59 SERS data for 1,4-phenylenedi-isocyanide gave characteristic YCNbands for C-bound molecules on colloidal gold particles.60 DFT calculations of vibrational wavenumbers for Cp2Zn confirm that (q5C5H5)* is not the preferred structure.61 Ab initio calculations on the HgCl,/HCdH system produced predicted vibrational wavenumbers for the possible n-complexes HgC12(HCCH),,where n = 1 or 2.62The Raman spectra of Sm,(C60),where x = 1 - 6, gave evidence for distortion of the C60 framew0rk.6~

\ Ph

4: Vibrational Spectra of Some Co-ordinated Ligands

Table 3 vCH/vCD vcc GCCH PCH

121

Ligand mode assignments for CI(H)A1C2H (lcm-’) (a’) (a’) (a’) (a”)

33 12.O(H) 2027.9 683.0 703.0

2584.6 (D) 1905.9 505.6 604.3

Matrix-IR data were reported and assigned (using H/D isotopic data) for Cl(H)AlCCH - Table 3. The data were consistent with q’-CCH ~o-ordination.~~ The complex (28) has IR bands from vC=C at 2108 and 2122 ~ m - ’ Gas-phase .~~ IR data for the Al+-benzene system are consistent with an A1+-(q6-C6H6) interaction.66 The IR spectrum of F c C H ~ C O O S ~ ( O C H ~ C Hwhere ~ ) ~ N ,Fc = ferrocenyl, gave a number of ligand mode a~signments.~~ The complexes (29),where R = Ph, l-naphthyl or 9-phenanthryl, all gave vC=C in the range 2136 - 2139 cm-’.68The IR spectra of ArCOCH2TeCN, where Ar = Ph, 4-BrC6H4 or 4-PhC~Hq6~ and (PhCOCH2)2TeX2,where X = Br or I,70all gave IR bands due to vC=O of the phenacyl group near 1650 cm- ’. 2

Xenon Complexes

The Raman spectra of the complexes [C~(X~F~),][ASF~]~, where n = 2.5 or 4, are dominated by vXe-F modes of the coordinated XeF2,i.e. 533,546 cm-’ for n = 4, 519, 528 cm-I for n = 2.5.71

3

Boron and Aluminium Donors

The IR spectrum of Mg(BH4)*.20Et2includes four vBH bands - suggesting the presence of double hydride bridges.72 DFT calculations have given vibrational wavenumbers for the tetrahydroborato ligand in [Ti(CO)4(q3-BH4)] - . 7 3 The matrix-IR spectra of M(BH4)4, where M = Zr or U, can both be interpreted in terms of monomeric, Td M[(V-H)~BH]~ )~ units.74Ab initio calculations of vibrational wavenumbers for Z T ( B H ~gave reasonable agreement with experimental IR and Raman data assuming q3-BH4 c0ordination.7~ The IR spectrum of (30) showed vAlCl bands at 424 and 412 ~ m - ’ Ab . ~ initio ~ calculated vibrational wavenumbers for Hf(BH4)4show that the published data are consistent with T molecular The following assignments were proposed from the IR spectrum of (31):vBH(t) .~~ 2428,2388 cm-I, vBH(br) 1773 cm-’, 6BH2 1174 cm-’, vNO 1675 ~ m - ’ For (32), where S* = timMe,Pip,and HtimMe,PiP= functionalised mecaptoimidazole, vBH(t) was seen at 2450 cm-’ and vBH . . . Re 2070 The complex U[~’-H(p-H)B(pz‘”~~~)(pz~~~~~~)]~ gave IR evidence for agostic B-H . . . U interaction, with vBH at 2440 cm-I, and a complex set of bands 2080 2280 cm-’.*’ Ab initio calculations of vibrational wavenumbers for Al(BH4)3gave

122

Spectroscopic Properties of Inorganic and Organometallic Compounds H

z'

cp

'i

\ZrCp2

I

(3 1)

reasonable agreement with experimental ligand modes assuming q2-coordination.81

4

Carbonyl Complexes

Adsorption of carbon monoxide on to Li-ZSM-5 gave the following IR bands (vC0): Li(CO)+ 2195 cm-'; Li(CO)2+ 2187 cm-l; Li(OC)+ 2102 cm-' and (OC)Li(OC)+ 2110 cm-'.82 IR spectroscopy (vC0) was used to monitor structural changes for CO adsorption on LiX-1.0 zeolite between 77 and 298 There is IR evidence for both M(CO)+ and M(OC)+ species (M = alkali metal) formed by the adsorption of CO on alkali-metal-exchanged zeolites.84 Thus, for M = Rb, IR bands were seen at 2161 cm-I and 2119 cm-' for Rb(CO)+,Rb(0C) re~pectively.8~ Adsorption of CO on BeNaY and MgNaY zeolites gave IR bands due to Be(C0)2+(2222 cm-') and Mg(C0)2+(2215 cm-') respectively. On MNaY, where M = Ca, Sr, Ba, there was evidence for M(C0)2+(2201 cm-' (Ca), 2193 cm-' (Sr), 2181 cm-' (Ba)), and M(OC)2+(2094 cm-' (Ca), 2097 cm-' (Sr), 2100 cm-' (Ba)). For the heavier Group I1 metals, IR bands were also seen due to tricarbonyl units.86 A separate report on CO adsorption on the zeolite SrY yielded the following assignments: Sr(C0)2+219 1 cm-'; Sr(OC)2+2095 cm-'; Sr(C0)22+2187 cm-'; Sr(CO)(OC)2+2098 ~ m - ' . ~ ~ Low-temperature adsorption of CO on Ti/Ti02 produced Ti(C0)4+ (vC0 2177 cm-'), CU(CO)~+ (2192 cm ') and CU(CO)~+ (2160,2110 cm-').88 The complexfuc-[( 12[ane]P3Et3)V(CO)3]-gave IR bands due to v C 0 at 1894, 1857 cm-'. Oxidation to the neutral, 17-electron analogue gave the expected increase in v C 0 wavenumbers, to 2098, 1962 cm-' for V(0).89Detailed assignments of v C 0 modes have been proposed for V("CO)6, where n = 12 or 13, from IR (gas) and Raman (argon matrix) spectra. There was evidence for Jahn-Teller distortion, lowering the symmetry to D3d.The mode of tl, symmetry for Oh gave +

~

4: Vibrational Spectra of Some Co-ordinated Ligands

123

two components, at 1972 cm-' (a2,)and 1970 cm-' (e,), with the a', and e, modes at 2072, 1960 cm-' respe~tively.'~ Laser-ablated Cr atoms react with CO/Ar to give matrix-trapped high-spin Cr(C0) (vC0 1975.6 crn-l), bent CI-(CO)~(1970.8, 1821.5 cm-'), as well as Cr(CO)+ (2200.7 cm-'), Cr(C0)2- (1705.0 cm-') and Cr2(CO)2(1735.4 cm-'). Assignments were supported by DFT calculations?' DRIFTS ( K O ) data were reported for (arene)Cr(C0)3synthesised within the confines of NaX zeolite. For arene = benzene there was evidence for two distinct sites for this ~ornplex.'~ IR spectroscopy (vC0) was used to follow photochemical reactions of (OC)4Mn(p-q3:q6-C3H4c6Hs)cr(Co)3 in frozen gas matrices at 12K.93TRIR data (vC0) were used to follow the isomerisation of M(CO)s(q'-DHF) to M(C0)5(q2DHF), where M = Cr, Mo, W; DHF = 2,3-dihydrof~ran?~ Laser-ablated M ( = Mo or W) atoms and CO gave neon-matrix-trapped MCO (vC0 1881.2 cm-I (Mo), 1859.9 cm-' (W)), M(C0)2(1895.2 cm-' (Mo), 1884.5 cm-l (W)). There was also evidence for M(CO),, where n = 3, 4 or 5, M(C0)1,2+,and M(CO)1,2-.95 The bridging carbonyl group in (33) has v C 0 at 1804 ~ m - ' . ~ ~

TRIR (vC0) was used to follow the photophysical changes of W(CO)4(l,2where alkyl ethylenediamine) and W(C0)4(N,N'-bis-alkyl-l,4-diazabutadiene), = Me or iPr.97Similar experiments were used to monitor reactions of the transient intermediates of the W(CO)5(cyclohexane)reactions with pyrrole and pyrrolidine?* The FTIR spectrum of CO adsorbed on Mn-ZSM-5 zeolite at 85 K showed that Mn(C0)2+(vC0 2214 cm-') was present, together with Mn(CO)?+ (2202 ~ m - ' ) .Redox ~ ~ processes in pyrazolate-bridged CpMn(C0h systems were followed by IR spectroelectrochemistry (vCO).'"O Similar studies were reported for the redox processes of fac-MnBr(CO)3(tmbp), [Mn(CO)3(tmbp)]2 and [Mn(C0)3(tmbp)]-, where tmbp = 4,4',5,5'-tetramethy1-2,2-ph0sphinimine.'~~ DFT calculations have been made of vibrational wavenumbers for Mn2(CO),, where x = 7 - 10.'O2 TRIR data (vC0) were used to probe the MLCT excited states for fac[Re(pp)(C0)3(4-Etpy)If, where pp = phen, bipy or substituted bipy, and cis[OS(~~)~(CO)(L)]"+, where pp = phen, bipy, L = PPh3,MeCN, py, C1, H, n = 1 or 2.'03 Raman spectroscopy (vC0) was used to follow thermal transformations of Re(CO)5Clsupported on zeolite Y, e.g. formation of Re(C0)3(o-Z)2.'04 Iron atoms and CO react to give argon-matrix trapped Fe2C0, whose IR spectrum contains v C 0 at 1898.0 cm-' (l2Cl60),1854.5 cm-' (13C160),1855.7

124

Spectroscopic Properties of Inorganic and Organometallic Compounds

cm-l

(12C 18O).lo5IR spectra show the formation of both on-top and bridged

carbonyl complexes on adsorption of CO on a four-monolayer thick Fe/Cu( 100) surface.'06 The species [(L)Fe"CO . . , Cu'CO]+, where L is a tetra-arylporphyrinate tethered to a tris-(2-pyridylmethyl)amine, shows vCO(Fe) at 1973 cm-' and vCO(Cu) at 2091 cm-l.lo7 FTIR spectroscopy (vC0) was used to monitor CO migration among internal cavities of the myoglobin mutant L29W.'08 The resonance Raman spectrum of the CO-adduct of deoxyMb (horse myoglobin) shows that this is six-coordinate. Mb-CO is also six-coordinate, and low spin, with the haem iron binding His93 weakly, if at all.lo9Resonance Raman spectroscopy was used to probe the CO binding kinetics to the six-coordinate iron(I1) haem of the amino-terminal domain of mouse-haem -regulated eIF-2a kinase.' lo TRIR (vC0) was used to identify the triply-bridged intermediate ( C P F ~ p)~( C0)2(p-CHMe)(vC0 1840,1808 cm-') produced by CO-loss from [CpFe(C0)2] (p-CO)(p-CHMe)."l An FTIR spectroelectrochemical study on [CpFe(C0)2]2 and related species has been reported.'l2 New calculations have been reported using a CO-factored force field for Fe(C0)5."3 The IR spectrum of adsorbed IR spectroscopy Fe(C0)5was used to characterise gold supported on ~ilica."~ (vC0) was used to follow the photochemistry Of ('Pr2NP)2COFe2(C0)6at 90 K. It was suggested that loss of P-bridged CO occurred, giving an intermediate of DZh symmetry.'' The IR spectrum of CO adsorbed on a Ru( 109)surface showed that an 'on-top' Ru-CO unit was formed, with a coverage-dependent v C 0 in the range 1973 2063 cm"."6 IR spectroelectrochemical studies have been carried out on the interaction of adsorbed CO with ruthenium-decorated Pt nanoparticles (Ru-CO and Pt-CO features were both ~ e e n ) . "IR ~ spectroscopy on co-adsorbed CO and H2 on Ru/A1203gave evidence for a hydridocarbonyl species with v C 0 at 2030 cm-'. The most stable species was Ru(CO), (n > l), with v C 0 at 1980 and 2060 cm-l

118

(3 5 ) (34)

The bridging carbonyls in (34) give v C 0 IR bands at 1750 and 1702 cm-.' '19 The presence of one bridging and one terminal v C 0 for (35), where R = tBu or SiMe3,confirm the trans configuration. For the CsPh5analogues, however, cis isomers were indicated.12' IR spectroelectrochemistry (vC0) was used to probe the electrochemical behaviour of R U ~ C ( C O ) ~ ~ ( ~ ~and - ~ related ~ , ~ ~spe,~~-C~~ cies.12'

4: Vibrational Spectra of Some Co-ordinated Ligands

125

TR3 was used to follow the redox processes for trans-(C1)[0~(bipy)(C0)(CH~CN)Cl~]~, where n = 0, +1, using both bipy and CO modes.122 The matrix-IR spectrum of Co2CO (from the Co atom and CO reaction) gives v C 0 at 1953.3 ~ m - ' . The ' ~ ~IR spectrum of CO and NO adsorbed on Co-ZSM-5 zeolite gave evidence for the formation of Co(CO), CO(CO)~,Co(N0) and C O ( N O ) ~The . ' ~ ~adsorption of CO on Co-ZSM-5 gave IR bands from CO(CO)~+ (2112,2042 cm-') and Co(C0)3+(2137,2089,2079 ~ m - ' ) . 'A~separate ~ report on the same system suggests that some Co2+/C0 species are formed, including CO(CO)~+ (2217,2207 cm-'), C O ( C O ) ~(2201 ~ + cm-l) and at higher CO concentrations, CO(CO)~+ (2130,2105,2075 cm-').'26 The IR spectra of T H F solutions of [Yb(THF)6][Co(C0)4]2include v C 0 due to the contact ion pair [(THF)xYb..0CCo(C0)3]+ at 1854 and 1898 cm-', together with v C 0 at 1887 cm-' from the solvent-separated ion pair.127Bands due to v C 0 have been reported for the new carbonyl cation [Co(CO),] +,of D3h symmetry: (al') 2195 cm-' (Raman), 2152 cm-' (IR);(a2")2140 cm-' (IR);(el) 2121 cm-' (IR and Raman).12' An IR spectroelectrochemical study (vC0) has been made of the reduction of C O ~ ( C O ) ~ ( ~ ~ - C O ) ( ~ where ~ - C ~ L2 H ~=) Lq4-C8H8, ~, q4-C6H8 or q4-6,6-Ph2C6H4.129 An ab initio calculation of vibrational wavenumbers has been carried out for Co2(CO)6(C2vsymmetry), HCO(CO)~, HCO(CO)~ (C2",C3vrespe~tively).'~~ FTIR (vC0) was used to probe the adsorption of CO on Rh/Si02 catalysts, showing the presence of several different active ~ites.'~' Fast TRIR was used to characterise CpRh(CO)(L) and Cp*Rh(CO)(L),where L = Xe or Kr, at room temperature in supercritical noble gas s o l ~ t i o n s .An ' ~ ~IR study of C O and N O adsorbed on Rh/A1203 gave evidence for the formation of Rh'(C0)2 and Rh(NO)+ species.133 CO adsorbed on Rh-MFI gives Rh(C0)2+(2114, 2048 cm-') and Rh(C0)3+ (2181,2118,2084 cm-').'34 The coordination of 1-hexeneto supported Rh(C0)2+ is consistent with the observation of v C 0 at 2053 ~ m - ' . 'The ~ ~ first definite spectroscopic characterisation of the elusive HRh(C0)4has been obtained, with v C 0 bands at 2041.6,2071.8 and 2123.6 c ~ l l - ' . ' ~ ~ The resonance Raman spectrum of [PhTttBu]Ni'(CO),where PhTt'" = phenyltris((tert-butylthio)methyl)borate, includes YCO at 1995 cm-I, showing significant Ni+CO ba~k-bonding.'~~ FTIR (vC0 for Ni(CO), species) was used to probe the nature of amorphous silica surface^.'^^ The IR spectrum of CO adsorbed on palladium particles grown on NaCl supports includes v C 0 at very low wavenumbers (1800 - 1550 cm-', i.e. very broad). It was suggested that this was due to Pd-CO-Na+ species.'39The FTIR spectrum of CO adsorbed on Pd/ceria catalysts shows the presence of linear Pd-CO, Ce'"-CO, bridged Pd(C0)2 and Pd2(C0)2 units.140IR spectroscopy (vC0) was used to characterise species formed by CO adsorption on Pd nanoparticles. There was evidence for bridge bonding by CO at particle edges and defe~ts.'~' FTIR spectroscopy was used to probe the interaction of CO with a Pt3Sn(111) surface. At different potentials both terminal and bridged CO were 0 b ~ e r v e d . l ~ ~

126

Spectroscopic Properties of Inorganic and Organometallic Compounds

DRIFTS data (YCO)were reported to characterise the Pt(CO), species formed by CO adsorption on titania-, alumina- and silica-supported Pt catalysts.'43 The IR spectrum of CO adsorbed on Cu( loo), (110)and (111)surfaces covered by sub-monolayers of Fe showed that the Cu(C0) interactions are altered by the presence of Fe, although no Fe(C0) interactions were detected.'44Adsorption of C O on to copper-exchanged ferrierite gave IR bands due to Cu'(CO), units (n = mainly 1 or 2).'45 Detailed IR and Raman spectra of CU(CO)+n(n = 1- 4), Ag(CO)+n(n = 1 - 3) and Au(CO)+. (n = 1,2) in a variety of strong acids showed that the dominant species for the catalysis of olefin carbonylation by such species are CU(CO)+~, Ag(CO)+, Au(C0)+2 re~pective1y.l~~ C O adsorption of C O on Cu-ZSM-5 showed the presence of three types of Cu+ site, with Cu+-COv C 0 wavenumbers at 2165,2160 and 2155 Another report on C O adsorption on Cu-ZSM-5 suggested that v C 0 values depended on the method of catalyst p r e p a r a t i ~ n . ' ~ ~ The adsorption of CO on Cu/MCM-48 leads to the formation of C U ( C O ) + ~ ( v C 0 2162, 2121 ~m-').'~' Laser-ablated copper atoms react with CS to give argon-matrix-isolated CuCS (bent - YCS 1187.2 cm-I), Cu(CS)2 (linear - YCS 1291.3 cm-') and CuCu(CS) (YCS1353.9 cm-I). These assignments were supported by DFT calculation~.'~~ FTIR spectroscopy (YCO) was used to probe the interaction of CO with Ag/a-A1203epoxidation catalysts, and the effect of Cs+ and C1- p r o m ~ t e r s . ' ~ ~ CO adsorbed on Au(ll0) at 300 K gave an IR band at 2110 cm-' due to Au(CO).'~~ I n situ IR spectroscopy of C O adsorbed on supported gold catalysts gave evidence for linear CO on an oxidised gold centre (2100 cm-'). It was also suggested that some bridged CO species were YCOvalues An IR band at 2269 cm-' was assigned as v C 0 for (F3C)3B(CO).154 were reported and assigned for B(C0)2 in an argon matrix (one product of the B atom + CO reaction) - Table 4.'55 Laser-ablated A1 atoms and C O react to give neon-matrix-trapped species which included the known Al(C0) and Al(CO)*, and also a dibridged unit A12(C0)*,with an IR absorption at 1727.9 ~ m - ' . 'FTIR ~ ~ spectroscopy (vC0) gave evidence for both Si-OH . . . C O and Si-OH . . . OC species for C O adsorbed on silica and ~ilicalite.'~~

Table 4

vC0 assignments for B(C0)2 (/cm-*) 1°B symm.

B(C0)2 B('2C0)('3CO) 2059.0 B( 3CO)2 B(C'60)(C180) 2072.4 B(C180)2

antisymm. 2022.5 1989.3 1976.3 2007.4 1993.9

'lB symm. 2055.8 2070.5

antisymm. 2004.9 1974.4 1959.6 1988.9 1977.7

127

4: Vibrational Spectra of Some Co-ordinated Ligands

5

Nitrogen Donors

5.1 Molecular Nitrogen, Azido- and Related Groups. - The complex (36) and related species gave IR bands due to vNH in the range 3200 - 3400 cm-'.I5* The IR and Raman spectra of [(P2N2)Zr]2(pq2:q2-N2), where P2N2 = PhP(CH2SiMe2NSiMe2CH2)2PPh, included vNN of the unit (37) at 775 cm-' (753 cm-' for "N).lS9

II

N

The complexes Mo(N&Pd, where P = PPh(OEt), or PPh2(OEt),give vN=N as single IR bands (2004,1990 cm-' respectively), consistent with trans geometry.16' Trans-M~(N~)(NCNR~)(dppe)~, where R = Me or Et, show vN=N at 1890 cm-I (Me) or 1910 cm-' (Et).161 IR data for [MF(NNH3)(depe)2]+, where M = Mo or W, depe = 1,2bis(diethylphosphino)ethane, gave the following assignments to hydrazidium ligand modes: v,NH 3315, 3265 cm-' (Mo); 3345, 3275 cm-' (W); v,,NH 3171 cm-' (Mo), 3178 cm-' (W).162The IR spectra of trans-R(Cl)MoO(NNPhR')(ophen), where R = R' = Me, Ph; R = Me, R' = Ph; R = Ph, R' = Me, all include vN = N in the range 1586 - 1592 ~ m - ' . ' ~ ~ The IR and Raman spectra of W(N2)(NCEt)(dppeh include a band due to vNN at 1895 cm-' (1836 cm-' for "N), together with vCN at 2190 c111-l.I~~

The IR spectrum of (38), where Ar = 2,4,6-iPr3C6H2,shows v N = N at 1812 .165 Polymeric [Mn(L)(N3)2],,where L = bidentate Schiff bases from pyridine-2-carbaldehyde with aniline and substituted derivatives, have IR bands due to vasN3at 2060 and 2100 cm-'. The former is due to two different types of bridging azido groups.166

cm-l

128

Spectroscopic Properties of Inorganic and Organometallic Compounds

IR bands were assigned to YNNmodes for [Fe(N2)(X)(depe),]+,where depe = Et2PCH2CH2-PEtZ7X = H or C1, i.e. 2091 cm-' for X = H, 2086 cm-' for X = C1 (both gave expected 15Nshifts, and were confirmed by ab initio calculation^.'^^ A temperature-dependent IR study of the spin-crossover complexes [Fe(L)6] (BF4)2,where L = alkyl-substituted tetrazole ligands, show significant changes in the number of ligand modes at the HS/LS transition.'68 DFT calculations have been made of vibrational wavenumbers for R u H ~ ( N ~ ) ( P HR~u)H ~ ,~ ( N ~ ) ~ ( and P H ~R)u~H ~ ( H ~ ) ( N ~ ) ((various P H ~ ) ~isorner~).'~~ The complex (39), where P-P = 2,3-bis(diphenylphosphino)butane,has YNN at 2155 cm-', showing only weak Ru-+N2 ba~k-bonding.'~'The complex [Ru(CH3N=NH)(CH3NHNH2){ P(OEt)3)4]2+gives vNH ligand bands at 3347, 3300 and 3295 cm-'.17' Y N = N for the complexes R u ( L ) ~ ~where + , L = (40), R = H, Me, OMe, C1, are near 1300 cm-' consistent with the coordination mode (41).172

w

NHAr

NH

(39)

The IR spectrum of tr~ns,tr~ns-[(terpy)Cl~O~~~(N~)0~~~Cl~(terpy)]-, where terpy = 2,2':6,2"-terpyridine, gave values for ~asN3for the 14N/15Nisotopomers Table 5.173 IR data for [ M ( 4 , 4 ' - b i ~ y ) ~ ( N ~ H ~where ) ~ ] ~ +M, = Co or Ni, show unidentate coordination by both l i g a n d ~ .The ' ~ ~ complexes [Rh(terpy)(L)(N3)I2+, where L = phen, bipy, show YasN3 at 2030 cm-' (IR) and vSN31330 cm-' (Raman).'75 The modes vasN3(2065 - 2090 cm-') and 6N3 (605 - 620 cm-') were assigned from the IR spectra of [Ni(py-X)4(N3]+,where X = H, 3-C1, 3-Br, 4-Me or 4-Et.176The IR and Raman spectra of [Pd3(m-N3)(p-P~)5]n show p-1,l-bridging coordination of the azido, and exobidentate coordination of pyrazole (= Pz) ligand~.'~~ Adsorption of N2on Cu-ZSM-5 gave an IR band at 2295 cm-' due to 'on-top'

Table 5

vasN3modes for tran~,trans-[(terpy)(C2)~0~'"]2(p-N~)

(/cm-')

4: Vibrational Spectra of Some Co-ordinated Ligands

129

Cu-N2 coordination. A feature at 2130 cm-' was now shown to be due to CO impurity.'78The complex Cuq(p - ~ a l e n ) ( p ~ , ~ - N shows ~ ) ~ ( NvasN3 ~ ) ~ of the bridging azido groups at 2062 and 2023 ~ m - ' . ' ~ ~ The IR spectrum of [Cd(02N-C6H4-NNN-C6H4N02)3]-shows coordination via N(l) and N(3) atoms of the triazenido group (YNNN1261cm-l, compared to 1407,1107cm-' for the free ligand).18' where n = The IR and Raman spectra of the azidoborates [(C~FS)C~B(N~)~]-, 1- 3, gave the following assignmentsto ~asN3modes: n = 1,2113 cm-' (IR),21 18 cm-' (Raman); n = 2,2121,2095 cm-' (IR), 2126,2090 cm-' (Raman); n = 3, 2132,2109 cm-' (IR), 2143,2131,2115cm-' (Raman).'" InC13(HL),where HL = (42), shows Y N = N of the coordinated ligand at 1320 cm-', compared to 1450 cm-' for free HL.IS2

The first report has been made on Si(N3)& The IR and Raman spectra were consistent with S6 symmetry and gave detailed assignments, e.g. ~asN32139 cm-l .183 Azido ligand modes were also assigned from IR and Raman data for AsCl(N&(py): vaS21 18 cm-' (in-phase),2085 cm-' (out-of-phase);vs 1268 cm-' (in-phase), 1258 cm-l (out-of-phase);6 670 cm-' (in-phase), 647 cm-' (out-ofphase). For SbCl,(N3)(Py)2,Yas was at 2091 cm-', Y, 1210 cm-' and 6 650/594 cm-l .184 For Me3Se(N3),~asN3 is at 2022/1996 cm-', with vsN3at 1321 ~ m - ' . ' ~ ~

5.2 Amines and Related Ligands. - Laser-ablated M (= Zr or Hf) atoms react with NH3 to give products trapped in argon matrices, including MNH3, for which 6,NH3 modes were assigned: 1156 cm-' (M = Zr), 1158.8 cm-' (Hf).'86 There is matrix-IR evidence for the formation of C12V(0)N-(H)C3H5from VOC13 + C3H5NH2, with YNHat 3362 ~ m - ' . 'Co-deposition ~~ of OVF3and NH3 in an argon matrix at 14 K produced a complex OVF3.NH3. Ligand mode assignments (Table 6) were supported by DFT and ab initio calculations.'88

The IR spectra of ReC13(L),where L = (43) and related ligands, contain vC02 bands showing 'free' carb~xylates.'~~ FTIR spectra for M(L)2Ni(CN)4,whereM = Fe or Zn, L = 4-aminopyridine, show that L is coordinated only via the ring,

130

Table 6 pNH3 WH3 6asNH3 YsNH3 YasNH3

Spectroscopic Properties of Inorganic and Organometallic Compounds

Ligand mode assignmentsfor 0 VF3.NH3 (lcm-’) I4NH3 644 1146/1200 -

3406

15NH3 638 1141/1195 1603 3300 3404

and not the NH2N at~rn.’’~ Resonance Raman spectra were used to probe the interaction of N-alkyl- and N-aryl-hydroxyguanidines with recombinant N O synthases. There was evidence for the formation of six-coordinate, low-spin, Fe(II1) spe~ies.’’~ IR and Raman spectra of the spin crossover complexes Fe(~y)[M(cN)~l, Fe(p~)[M(cN)~l, where M = Ni, Pd or Pt, py = pyridine, pz = pyrazine, gave assignments to ligand modes. There were some significant changes between HS and LS states, especially for Gring modes of P Z . ~ ’ ~ Picosecond TR3 studies were used to probe the photophysics of R~(bipy)~’+ and its deuteriated isot~pomer.’’~ The IR spectra of RuC12(bipy)(L),where L = (44), R = H, Me, C1 or N02, include vNH bands in the range 3400 - 3420 cm-’, confirming the presence of amine NH groups.’94 DFT calculations were used to assign vibrational modes for pyridine adsorbed on a number of metals, e.g. Ni, Pd, Pt, Cu, Ag, Au etc. (bands observed by SERS). It was shown that the value of v6 (a deformation mode near 600 cm-’) was a good indicator of the strength of the M-py intera~tion.’~’ The IR spectrum of ([Ni(py~)(H20)4](N03)2.2H20),included bands characteristic of bidentate bridging pyrazine (= pyz) ligand~.’’~

(45)

DFT calculations of pyridine internal modes ( ~ 1 7v3, ~ , v5, v18b) for py coordinated to Pt, Cu, Cu+, Ag, Ag+, Au and Au+ were used to improve assignments to ligand modes for such species.’97IR spectra for a range of metal(I1) halide benzimidazole ( = benz) complexes, e.g. M(benz)Xz,M = Cu, Cd, X = C1 or Br; C ~ ( b e n zand ) ~ C o ( b e n ~ ) ~X X ~=, C1, Br or I, gave characteristic ligand mode assignments. For C ~ ( b e n zthe ) ~ data were consistent with the formulation (45).”* For Zn(benz)’C12 the IR spectrum shows tetrahedral coordination, with

4: Vibrational Spectra of Some Co-ordinated Ligands

Table 7

131

Ligand mode assignments for H g ( N H 3 ) 2 +(lcrn-')

y1

(ys)

y2

(6s)

y3

(VaJ

(a11 (ad

3290 (Raman) 1253 (IR) 3385 (IR)/3378 (Raman) 1612 (IR) 694 (IR)

(4 (e)

V4

(PI

N-coordinated benzimidaz01e.l~~ Ligand (NH3) modes have been assigned from the IR and Raman spectra for Hg(NH3)42+,in a local symmetry environment of C3" - Table 7.200Resonance Raman spectroscopy was used to examine the nature of a novel CT ground state in (C5Me5)Yb(bipy). The data were consistent with the presence of bipy -, i.e. the reduced radical anion.2o1

5.3 Ligands Containing >C = N- Groups. - Resonance Raman bands due to porphyrin ligand modes in M(P),where M = Mg(II), Ni(II), Cu(I1) and Zn(II), P = phenylethynyl-substituted porphins, were used to probe non-planarity of the core macrocycle.202

I

/-

The complexes (46),where R1 = Me, R2 = Me, Ph, Ph-2-OMe; R' = Ph, R2 = Me, all show v C = N in the range 1580 - 1600 c1~1-l.~'~ DFT calculations on low-lying excited states of W(C0)4(MeDAB),where MeDAB = N,N'-dimethyldiazabutadiene, W(CO)5(py) and W(C0)5-(CNpy),where CNpy = 4-cyanoyridine, gave vibrational wavenumber prediction^.^'^ FTIR spectroscopy (ligand modes) was used to study the chloride cofactor in the photo-synthetic oxygen-evolving complex.2o5IR data (amide-I band near 1650 cm-') were used to follow thermally-induced changes in the secondary conformation of superoxide dismutase containing Mn, Cu/Zn or Fe.'06 Resonance Raman data (ligand modes) were assigned for BrRe(C0)4(daad), where daad = 2.6-diaza-anthracene-9,lO-dione, showing that coordination occurs via one ring nitrogen atom, and that the HOMO and LUMO are metal dn and ligand n* (localised on the quinoidal ring) re~pectively.~'~ TRIR and TR3 measurements were reported for fa~-[Re(CO)~(dppz)(py)] +,where dppz = dipyrido[3,2-a:2',3'-c]phenazine on pico- and nanosecond timescales.208 TR3 (nanosecond) was used to study the vibrational dynamics in five-coordi-

132

Spectroscopic Properties of Inorganic and Organometallic Compounds

nate high spin iron(I1) octaethylporphyrin with an axial 2-methylimidazole ligand.209Resonance Raman spectroscopy was used to probe the conformational properties of iron-zinc hybrid haemoglobin.210Stopped-flow FTIR spectroscopy gave information on nitromethane oxidation by the diiron(1V) intermediate of methane mono-oxygenase?" Resonance Raman data gave information on structural heterogeneity in M y cobacterium tuberculosis cata1ase-peroxidase?l2 Similar data for cellobiose dehydrogenase with Mef5 replaced by histidine shows that the iron(II1) form is low-spin at 90 K, and mixed HS/LS at ambient ternperaf~re.~'~ ATR-FTIR data (ligand modes) were used to characterise the P M and F intermediates of bovine and Paracoccus denitrijkans cytochrome c ~ x i d a s e . ~ ' ~ Ligand mode marker bands in the resonance Raman spectrum of the CObound P-subunit of Hb M Boston were used to monitor structural changes on ~oordination?'~ Smilar data were used to probe structural differences between wild-type and Y96F mutant forms of cytochrome P450,, (CYP 101), both with and without bound camphor or styrene substrates.216 The resonance Raman spectrum of cytochrome P450 (CYP 121) from Mycobacterium tuberculosis included marker bands showing it to be predominantly low-spin and containing a cysteinate- and water-ligated haem iron217Similar results on a new cationic peroxidase from fresh flowers of Cynara scolynus L., show that the Fe(II1) form was six-coordinate, high-spin, with H 2 0 as the sixth ligand.218 Resonance Raman spectroscopy for haem oxygenase from Pseudomonas aeruginosa suggests that haem-iron ligation is homologous to that for other a-hydroxylating haem oxygena~es.~'~ Conformational differences in Mycobacterium tuberculosis catalase peroxidase and its S315T mutant were revealed by resonance Raman spectra.220 An IR band due to a totally-symmetric (a3 mode of pyrazine (pz) in mixedvalence clusters { Ru30(OAc)6(L)(CO))2(p-pz)-,where L = py or substituted derivatives, was shown to be a useful probe for electronic coupling between the clusters.221Resonance Raman spectra of [R~(biq)~(box)] +,where biq = 2,2biquinoline, box = 2-(2-hydroxyphenyl)benzoxazole with 457.9, 514 and 632.8 nm excitation were used to assign low-energy electronic transitions.222TR3data for Ru(bpdz):+ and R~(bipy),(bpdz)~+, where bpdz = 3,3'-bipyridazine gave insights into the photophysics of these complexes. For the former, bands due to the bpdz - radical were seen.223 FTIR and Raman spectra of Ni(dmg)2,where Hdmg = dimethylglyoxime, gave detailed ligand mode assignments, supported by DFT calculations.224The IR spectra of (47a), where N-N = (47b)and related ligands, included YCNin the range 1590- 1690cm-' - typical of a-di-imine coordinated in an s-cis-conformat i ~ n Detailed . ~ ~ ~ ligand mode assignments were obtained for Ni"(TAA), (48), from IR, resonance Raman and SERS data, backed up by ab initio calculations.226 DFT calculations gave vibrational wavenumbers and a force field for Ni(OEP)?27Photochemical processes for Ni(TPP) + piperidine were followed Resonance Raman spectra of regioisomers of Ni(I1) benzoetioporby TR3.228

133

4: Vibrational Spectra of Some Co-ordinated Ligands

phyrin show significant differences in the low- and middle-wavenumber ligand bands, allowing the isomers to be differentiated.229 FTIR and FT Raman spectra were reported for M(P), where M = Ni, Cu or Zn, P = 2-nitro-tetraphenylporphyrin, enabling marker bands to be identified, due to vsN02(1323 - 1339 cm-'), vasN02(1516 - 1526 cm-') and vCp-N (961 971 ~rn-~).*~O Resonance Raman ligand mode markers for non-planarity in nickel and zinc tetra-alkylporphyrins correlate with deformations calculated by molecular dynamics methods.23'Resonance Raman ligand marker bands were used to probe structural changes in redox processes for methyl coenzyme M reduct a ~ e . ~ ~ ~ SERS data were used to characterise palladium phthalocyanine evaporated thin solid R I

The complex (49) gives an IR band due to vC = N of the coordinated ligand at 1539 cm-', together with vNH at 3326 cm-1.234Resonance Raman bands for the first electronic transition of ('Pr-DAB)Pt(CH3)2,and its CD3 analogue, where

134

Spectroscopic Properties of Inorganic and Organometallic Compounds

'Pr-DAB = N, N'-di-isopropyl- 1,4-diazabutadiene, include v,CN at 153 1 cm- ' (CH3), 1528 cm-' (CD3), showing that the electronic transition involves the a-di-imine ligand.235 Interactions involving two copper porphyrins, copper tetrakis(4-N-methylpyridy1)porphyrin and copper tetrakis(4-sulfonatophenyl)porphyrin, were studied by examining Raman band shifts in porphyrin ring modes.236UV resonance Raman spectroscopy was used to study the pH-dependent metal-release processes for Cu(1) and Cu(I1)p s e u d o a ~ u r i n s . ~ ~ ~ Several reports have been made of IR and resonance Raman spectra of lanthanide complexes containing naphthal~cyanines?~~-~~' The complexes (50), where Ln = Nd, Gd, Yb; R = Me or Ph, all show YC= N near 1640 cm-', from the y2-amidinate l i g a n d ~ . ~ ~ '

5.4 Cyanides, Isocyanides and Related Complexes. - The complex Nb[H(tBuL)I2Cl(NCMe),where H$Bu-L) = 2,6-bis(4-methyl-6-tert-butylsalicyl)-4-tertbutylphenol, has vCN of the coordinated NCMe at 2280 cm-'(cJ: 2251 cm-' for the free ligand)?42The cyano-ligand in M O ( ~ . - C ~ ) ( ~ ~ C ~ ~ ) ( C O ) , ( ~ ~ - C ~ H ~ ) ( gives vCN at 2291 ~ r n - ' The . ~ ~vCN ~ bands in the IR spectra of (51), where E = Si, Ar = Ph, C6F5,R = 'Bu, Cy, Ph, etc; E = Ge, Ar = Ph, R = 'Bu, are all at wavenumbers more than 100 cm-' less than for the free ligands, due to extensive Mo +C back bonding.244

The vCN modes for [Mn2(H20)2(CH3C02)][W(CN)s] give a single IR band at 2176.5 cm-', showing that all of the CN groups are equivalent, and that there is some bridging interaction between Wv and Mn1r.245 IR bands due to vCN are seen at 2060 and 2070 cm-' for [Re(tripho~)(CN)~]+, where triphos = l,l,ltris(diphenylphosphinomethyl)methane,compared to 2050 cm-' for free CN-.246 The coordinated cyano group in [(SBPy3)Fe(CN)]+, where SBPy3 = N,Nbis(2-pyridyl-methyl)amine-N-ethyl-2-pyridine-2-aldimine, has an IR band at 2073 cm-'.247The bridging YCN mode (2021 crn-') in [Cp(dppe)FeCNRu2(ap>4]+,where ap- = 2-anilinopyridinate, is shifted by about 50 cm-' to lower wavenumber compared to the monomeric iron

4: Vibrational Spectra of Some Co-ordinated Ligands

135

IR spectroscopy (vCN) was used to probe the conformational states of CNbound horse rnetmyogl0bin.2~~ The FTIR spectrum of cyanide-bound human haemoglobin shows three vCN bands, consistent with the presence of three conformational states (2116,2122,2127 cm-' -all showing the expected shifts for the I2Cl5Nand I3Cl4Nforms.250The FTIR spectra of the ferrocyanide adduct of superoxide reductases from Treponoma pallidurn and Desulfovbrio vulgaris have vCN at 2095 cm-' due to a bridging Fe-NC-Fe unit.251

(52)

The terminal cyanides in (52) give IR bands due to vCN at 2145 and 2133 .252 The q'-N-coordination of MeCN ligands in (MeCNhFe(SSiPh3) is shown by the observation of vCN at 2304 and 2276 cm-' (cJ:2250 cm-' for the free ligand).253Characteristic shifts of vCN to higher wavenumber occur on + Cand formation of the complexes FeC12(t - B ~ D i s N c ) ~[,A ~ ( ~ - B U D ~ S N )~] PdC12(t-BuDisNC)2,where tBuDisNC = di-i~onitrile.2~~ The vCN bands in the IR spectrum of [Fe(bipy)2(CN)4Cu2]show the presence of more than one type of bridging cyanide.255The bridging CN groups in [Fe1I2CuXI2( p-CN)4(dmbpy)4(impy)2]4, where dmbpy = 4,4'-diethyl-2,2'-bipyridine, impy = 2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-l~-imidazolyl1-oxy,give vCN at 21 19 cm-' in the IR spectrum.256There is IR evidence for both terminal and bridging cyano-groups in { (H30)[Ni(H2L)]2[Fe(CN)6]2[Fe(CN)6.6H20},.257 cm-l

+

The complex (53) gives vCN at 2298 ~ m - ' . ~IR~ (YCN) * spectroelectrochemistry was used to follow redox-activated ligand-exchange reactions of trans[NBQ][RUX~(CNX~~)~], where X = Cl or Br.259The bridging dicyanamide ligands in [{Cp(PPh3)2Ru}2N(CN)2]+give IR bands due to vCN at 2295 and 2208 cm-', consistent with a-donation and mback-donation to the ruthenium unit.260vCN bands for [{(Ph3P)3Cu(NC)2}2R~(bipy)2]2+ and related species show

136

Spectroscopic Properties of Inorganic and Organometallic Compounds

characteristic increases compared to the parent complex R ~ ( b i p y ) ~ ( C N ) ~ . ~ ~ ' The IR spectra of M(N = C =N-2,6-R2C6H3)2L2,where M = Ni, Pd or Pt, R = Me; M = Pd, R = Et, L = PMe3 or PEt3, all show v,,N=C=N of the carbodi-imido ligands in the range 2098 - 2179 cm-1.262The IR spectrum of Ni(en)2[Au(CN)4]2.H20 gives vCN bands due to both terminal (2190,2180 cm-') and bridging (2214, 2202 cm-') cyano g r o ~ p s . 2The ~ ~ high-pressure Raman spectra (vCN) of the spin-crossover complexes Fe(pyrazine)[M(CNb].2H20, where M = Ni, Pd or Pt, gave evidence for pressure-induced spin tran~itions.2~~ IR spectroscopy (vCN) was used to probe the electrochemical properties of A SERS study of CN- adsorption at a platinum palladium hexa~yanoferrate.2~~ surface was used to follow the concentration dependence of the adsorption behaviour?66TRIR was used to investigate the nature of the lowest excited state of Pt1*(dpphen)(CN)2, where dpphen = 4,7-diphenyl-1,lO-phenanthroline,using vCN. It was suggested that the excited state is a x-n*intraligand The resonance Raman spectrum of the haem a3-C=N-Cub2+complex of oxidised cytochrome aa3oxidase includes vCN at 2151 cm-' from the Fe-C=Ntren = (54), has two CuBunit.268The complex [(tren)Cu-CN-C~(tren)]~+,where vCN bands in its IR spectrum, at 2182 and 2163 cm-'. Two features are seen because there are two independent ions in the unit cell. The wavenumber values are at the high end of the range for such bridging c y a n o - g r ~ u p s . ~ ~ ~

Several heterobimetallic coordination polymers have been prepared, incorporating [M(CN)2]-, where M = Cu or Ag, and [Ag2(CN)J- units. Characteristic vCN bands were identified in their IR spectra. Thus, for [C~(en)~l[Ag~(CN)~1 [Ag(CN)2], v(Ag)-CN is at 2140 cm-', v(Ag)-CN-(Cu)at 2156 cm-' and v(Ag)CN-(Ag) at 2118 ~ m - ' . ~The ~ ' IR spectra of [Cu(L)(dca)J,, where dca = dicyanamide anion, L = 2,2'-dipyridylamine or 1,2-bis(4-pyrrolyl)ethane,include three vCN bands due to the dicyanamide ligand (near 2330,2245 and 2174 cm-'), due to the bridging nature of the bonding.271 Raman bands due to vCN for Au(CN)~- doped into KCl are at higher wavenumbers than for pure KAu(CN)2 The compounds oC6F4(HgCN)2,n ~ - c ~ F ~ ( H g c C6F5HgCN N)~, and C6F4H(HgCN)all show IR bands from vCN in the range 2170 - 2183 cm-'.273 The IR spectra of Ln(DMF)4(H20)3(p-CN)M(CN)5, where M = Fe or Co, Ln = all lanthanides except Pm, Lu, all show vCN showing both terminal and

4: Vibrational Spectra of Some Co-ordinated Ligands

137

bridging cyano-gro~ps.2~~ The complexes (59,where Ln = Yb, Dy or Gd, have an IR band near 1630 cm-' from the q2-guanidinate(vNCN)?~' IR and Raman spectra of AlC13in CD3CN solution show shifts in vCC, vC=N and GCCN modes of the CD3CN due to donor-acceptor interactions with the Al.276Similar results were obtained from the GaC13/CD3CN The Raman spectrum of [Tl(en)2CN]2+in the solid phase gives vCN at 2148 cm-', showing the presence of a bridging cyanide ligand.278The Raman spectrum of T1S(C03)2(CN) has YCN bands at 2039, 2008 and 1996 cm-', with vSCO3 1041/1022 cm-', 6C03696/670/652 cm-' and yC03 853 cm-'.279 5.5 Nitrosyl Complexes. - The complex (56) has vNO at 1601 cm-' in the IR spectrum, compared to 1543 cm-' for the V(C0)2N0

(56)

The cationic complex [W(CO)(NO)2]2+in fluorosulfonic acid gives v,NO at 1845 cm-', v,,NO 1763 cm-' and v C 0 2150 cm-1.281NO adsorbed on reduced W03-Zr02catalysts forms W'+(NO) (vNO 1855 cm-') and W4+(NO)2(1785, 1700cm-1).282 Another report on NO adsorption, on W03-Zr02itself, suggested that surface nitrates were formed (IR bands at 1650, 1570 and 1230 cm-') together with a nitrosyl species with vNO at 1936 The IR spectrum of ReC12(NO)(py)3 contained a vNO band consistent with linear coordination of NO+ to the For ReX3(N0)(0AsPh3)2, where X = C1 or Br, vNO bands were at 1721 cm-' (Cl) or 1738 cm-' (Br), consistent with greater n-acceptor character for Br.285 In situ DRIFTS measurements have been reported for NO adsorbed on Fe-ZSM-5, e.g. Fe2+(NO)1877 cm-'.286TRIR data (vNO) were used to probe the bonding in two metastable states (MS1, MS2) of [Fe(CN),N0l2- (GS 1960cm-', MS1 1835 cm-', MS2 1664 cm-1).287 The IR spectra (vNO) of {Fe(NS3)(NO))Ni(R)(dppe), where R = C1 or CH3, NS3 = N(CH2CH2S)3,are both consistent with the presence of a formally NO- ligand (1666 cm-1).288A similar result was reported for [Fe(NS3)(NO)]- (1621 ~ m - ' ) . ~ ' ~ The complex (57) has vNO from the terminal nitrosyl group at 1692 cm-1.290 Values of vNO for nitrosyl complexes of (58) and related species show a good correlation between the wavenumbers and the electronic influence of equatorial ligand~.~~' The bent Fe-N-0 group in (nitrosyl)iron(II) deuterioporphyrin IX gives a

138

Spectroscopic Properties of Inorganic and Organometallic Compounds COOEt

vNO band at 1651 cm-'.292DFT calculations gave vibrational wavenumbers confirming the formation of dinitrosyl complexes M(P)(N0)2,where M = Fe or Ru, P = TPP, OEP or tetra-m-t0lylporphyrin.2~~ The resonance Raman spectrum of the N O complex of human haem oxygenase-I (hHO-I) shows that it is Fe3+,six-coordinate and low-spin, with vNO (IR) at 1918 The resonance Raman spectrum of the nitric oxide complex of reduced superoxide reductase from pyrococcus furiosus include vNO at 1721 cm-', consistent with a bent Fe-N-0, trans to cysteinyl s, in a six-coordinate arrangement.295NO bound to cytochrome cbb3 oxidase from P. stutzeri has vNO at 1903 cm-'.296TR3 data were used to follow the nitric oxide reduction catalysed nitric oxide reductase from Fusarium oxysporum, i.e. reduction of the Fe"'-NO comThe complex trans-[RuC1(N0)(bpydip)l2+,where bpydip = N,N'-bis(7methyl-2-pyridyLmethy1ene)-1,3-di-iminopropene, has vNO at 1920 cm- I, showing the ligand is formally NO+.297A value near 1950 cm-' for YNO for L = py, 4-picoline or 4-acetylpyridine, leads to the same [R~L(bipy)~(NO)l~+, conclusion for these complexes.299The IR band at 1561 cm-' for vNO in [RuCp(NO)(PPh3)2].+is over 100 cm-' lower than in the dication, confirming reduction of the N O ligand.300 The vNO values have been assigned from the IR spectra of cis-RuCl(qn)(NO), where Hqn = 2-methyl- (1835 cm-') or 2-chloro-8-quinolinol (1850 cm-I). These are consistent with the greater electron-withdrawing power of Cl.301The complexes [Ru(NO)(salen)(L)]",where L = C1, n = 0; L = H20, n = 1 +, have vNO values of 1838 cm-I, 1855 cm-' respectively - consistent with linear Ru-N-0 (H2salen = bis(~alicylaldehyde)ethylenediarnine)?~~ A similar observation was made for [R~(q'-phpy)(terpy)(NO)]~+,where phpy = 2-phenylpyridine, terpy = 2,2':6',2"-terpyridine (1858 ~ m - ' ) . ~ ' ~ Redox processes for trans-[R~Cl(NO)(dppe)~]~+ were followed by IR spectroscopy in the vNO region.304The IR spectra of (por)Ru(PhN0)2,where por = T P P or tetra-p-tolylporphyrinato, have vNO near 1348 cm-I. Replacement of one PhNO by 1-MeIm leads to a reduction of 27 cm-' in this value.3o5The IR band due to vNO in [ R ~ ~ 0 ( 0 A c ) ~ ( p y ) ~ ( NisOat ) ] 1865 + cm-', i.e. linear Ru-N0.306

Adsorption of N O on Co/S02--Zr02 forms a mononitrosyl (vNO 1922 cm-I)

4: Vibrational Spectra of Some Co-ordinated Ligands

139

and a dinitrosyl (1903, 1814 c ~ - ' ) . ~ O ~ There have been several reports of IR @NO) spectroscopy being used to study the adsorption of N O on CO-ZSM-~.~'~-~'' vNO bands were assigned from the IR spectra of (RN=CHCH =NR)Co(NO)(CO), where R = 'Pr (1684 cm-I), 2,6-'Pr&& (1707 cm-') and p-CH3C6H4(1695 ~ m - ' ) . ~ ' ' Adsorption of NO from NO/CH4/02mixtures on to 2%Pd/Ti02 gives an IR band at 1775 cm-' from Pdo-NO (linear) at 1775 cm-', with another at 1666 cm-' due to a bent Pd-N-0 unit.312. N O adsorbed on CuO/Zr02 forms Cu+(NO) (vNO 1759 cm-') and Cu2+(NO)(1872 ~ m - 9 . ~A ' similar ~ study for N O on Cu+-ZSM-5 suggested formation of Cu+(NO)(vNO here assigned as 1810cm-') and Cu+(N0)2(1826 cm-', vas; 1732 cm-', vs).314

6

Phosphorus and Arsenic Donors

The IR spectra of the complexes CpMC&(PH2R),where M = Nb or Ta, R = tBu, Cy, Ph, mesityl, show vs and ~asPH2in the range 2375 -2411 cm-'.315 IR and Raman spectra gave assignments (supported by ab initio calculations) for the P(CF3)2- ligand modes in [W{P(CF&}(CO),]-, e.g. ~as/~sPC2 455 ~ m - ' . ~ ' ~ Bands due to vPH were seen for W(C0)5[PH(C6F5)2]at 2400 cm-' (IR) and 2411 cm-' (Raman), about 30 cm-' higher than in the free ligand.317The complexes (OC)5W(H2EBH2.NMe3),where E = P or As, both gave characteristic vEH and vBH modes, e.g. for E = P, vPH 2319 cm-', vBH 2423 cm-'; As, vAsH 2065 cm-',vBH 2125 ~ m - ' . ~ ' ~

The complex (59)has v P = 0 in the IR spectrum at 1155 ~ r n - ' . ~ The ' ~ IR bands due to v P = S in (60) and related species are all near 634 cm-', showing 'free' P=S, and unidentate coordination as shown.320For (61), where E = 0 or lone pair, v P = N is at 931 cm-' (0),920/906 cm-' (lone pair), with v P = O at 1214 cm-' for E = 0.321

140

Spectroscopic Properties of Inorganic and Organometallic Compounds

The IR spectra of MC12[(C4H3S)3A~]2, where M = Pd or Pt, include vAsC of the ligand at 472 ~ r n - ' The . ~ ~IR~ spectra of AuX(PPh2C=CH),where X = C1 or Br, gave the following assignments: vCH 3275/3245 cm-' (Cl), 3275/3172 cm-' (Br);vC-C 2056 cm-' (Cl), 2049 cm-' (Br).323 7

Oxygen Donors

7.1 Molecular Oxygen, Peroxo, Aquo and Related Complexes.- Adsorption of ozone on to MgO gave an IR doublet 1105/1024 cm-' due to Ys/Vas of O3 adsorbed through a terminal oxygen to Mg2+at the surface.324 The Raman spectrum of [Ti2(02)2(cit)2]4-, where cit = citrate, includes v 0 0 at 880 cm-' for the peroxo group.325The q2-peroxoligands in [Nb(02)2(edta02)]2gave IR bands at 870 and 855 cm-'. Carboxylate modes were seen at 1619 cm-' (~asC02)and1443 cm-'(v,C02).326 IR and Raman spectra were reported for [Cr(02)4]3-,with YOObands seen at 838 cm-' (Raman) and 813 cm-' (IR).327The complex Cp*(02)(0)W-C~C-C=CH has v 0 0 of q2-02 at 852 cm-', with YCPC bands at 2010 cm-' (W-C=C) and 2160 cm-' (CECH).~~' Resonance Raman data for [(N4Py)Fe'"(q'-00H)]2+ (790 cm-') and [(N4Py)Fe"'(q2-02)]+ (827 cm-') included YOO bands as shown (N4Py = N,N(173)-bis(2-pyridylmethyl)-~-bis(2-pyridylmethylamine)~29The cluster complex [Fe4(0HO)(OH)2(02CMe)4(phen)4]3+ has YOH(of bridging OH-) near 3580 cm-', (of bridging OHO-) 3070 cm-'. Carboxylate modes were consistent with bidentate acetate l i g a n d ~ . ~ ~ ' The Raman spectrum of [Fe'"(L)(OOtBu)] +,where L = hydrotris(3-tertbutyl-5-isopropyl- 1-pyrazolyl)borate, includes v 0 0 (coupled with vCC) at 889 and 830 ~111-l.~~' For [(L)Fe(00'Bu)I2+,where L = aryl substituted tris(2pyridylmethyl)amine, have YOO of the peroxo ligand in the range 818 - 876 cm-1 332 Oxygenated twin-coronet porphyrins show YOO near 1140 cm-' (from an Fe02 IR and Raman spectra of an Fe"'-OOH intermediate for the cysteinate-ligated non-haem iron enzyme superoxide reductase include v 0 0 at shifts).334 784 cm-' (identified by 160/'80 The complex [Co2(p-OH)(p-OAc)(OAc)2(dipyam)2] +(OAc)-, where dipyam = 2,2'-dipyridylamine, shows YOH of the bridging hydroxyl ligand at 3418 cm-', together with bands from ionic, unidentate and bridging bidentate acetate The Raman spectrum of the oxygenated binuclear Co(I1) complex of P-alanyl-L-histidine shows the presence of both (62) and (63) An IR band due to vOH of the H20 ligands is seen at 3442 cm-' for [C0(4,4'-bipy)(H~O)~](4abs), where 4-abs = 4-aminobenzene ~ u l f o n a t e . ~ ~ ~ The IR band due to vOH in (64), where N-N = bipy, Me2bipy,phen etc., is seen in the range 3610 - 3605 cm-1.338 The resonance Raman spectra of [{(R-TMPA)CU")(O')]~+gave v 0 0 of the unit (65) as follows: 827 cm-' (R = H), 822 cm-' (MeO), 812 cm-' (Me2N) (all identified by isotopic shifts).339 The mononuclear superoxo complex

4: Vibrational Spectra of Some Co-ordinated Ligands

-Pd-

I OH

141

C6F j

0 (65)

(64)

[Cu*(Mebtren)(02)], where Me&en = t ris(2-methylamino-meth yl)amine, shows a resonance Raman band from v 0 0 at 1122 cm-'. For ([(Me6tren)-cU1] 4 0 2 ) ) +, v 0 0 of the peroxo group is at 825 ~ m - ' . ~vOH ~ ' is seen at 3306 cm-' in the IR spectrum of C U ~ ( O H ) ~ F ~ . ~ ~ ' The p3-q2:q2:q2-(02-) ligand in Gd4(02)2C18(py)10 has an IR band from v 0 0 at 824 The Raman spectra of corrosion products formed on UO2 nuclear fuel during leaching experiments contain a band at 870 cm-' due to v 0 0 for the peroxide U04.343 +

7.2 Carboxylate and Related Complexes. - The complex anion [Be40(cO3)6l6- shows the expected bands for bridging, bidentate carbonato ligands (v,C-0 1061 - 1169 cm-'; v,C=O 1500 - 1601 ~ m - 9IR . ~photodissociation ~ spectroscopy of Mg+(C02), clusters gave data consistent with a linear structure for n = 1, bent for = 2 and trigonal pyramidal for n = 3.345There is IR evidence for coordinated carboxylate (to Ca2+)in adsorbed calcium oleate and teara ate.^^^ The IR spectrum of (V'V0)2(p-OH)(p-OAc)(p-H~mpg-S,S)2(bipy)2, where H3mpg = sulfhydryl-containing pseudopeptide, includes v,,C02 1557 cm- ', ~ $ 2 0 21386 cm-' from the bridging acetate.347 The complex (66) has ~asC02at 1590 cm-', v,C02 1425 cm-' and YasCOC 1136 cm-' from the oxydiacetato ligand.348The IR spectrum of Nb(OMe)4[OC(0)OMe] has bands from the hemicarbonate ligand consistent with ~ l ~ - c h e l a t i o n . ~ ~ ~ 0

142

Spectroscopic Properties of Inorganic and Organometallic Compounds

The IR spectrum of [M0204(C204)Cl?-]n contains bands from unsymmetrically bis-bidentate oxalate ligands (both Va, and v,C02 are seen as two bands).350 The resonance Raman spectrum (676.5 nm excitation) of ( ~ B u C O ~ ) ~ W ~ ( ~ 02CC6F4C02)W2(02CfB~)3 shows enhancement of 6,C02 of the bridging group at 518 ~ m - ' . ~ ~ ' Characteristic vC02 IR bands for bridging carboxylate groups were observed for the complex Re2[02CCCHCO2(C0)6]4cl2 (1540, 1415, 1326 ~ m - 9 . ~ ~ ~ Fe+(C02), clusters were studied by IR laser vaporisation in a pulsed nozzle cluster source. vasC02in small clusters was shifted to higher wavenumbers than for free C02.353 The complex [Fer1'(tnpa)(0H)(CH3C02)]+,where tnpa = tris(6neopentylamino-2-pyridylmethyl)amine,has IR bands assigned as follows: ~asC021600 cm-', v,C02 1320 cm-',vCC 908 cm-', 6OCO 655 cm-', p,COO 508 cm-'. Assignments were confirmed by isotopic The IR spectra of Fe30(0A~)3(02CR)3(EtOH)3 and Fe30(02CR)6(EtOH)3, where R = C7H15, CllH23, C1&, gave assignments to vC02 modes for bridging carboxylate~.~~~ The IR spectra of (HL)ClFe(ox)FeCl(HL)and (HL)Cu(ox)Cu(HL),where H2L = tridentate ONN Schiff base hydrazine ligand, ox = oxalate, showed bands due to bridging tetradentate oxalate l i g a n d ~Oxalato . ~ ~ ~ ligand modes were also assigned from the IR spectra of [ML][Fe"Fe111-(~~)2(H20)]n, where M = Zn or Cd, L = 2-{ [2-(aminoethylamino)ethylirnino]methyl}phen01!~~IR spectra (vC02) of [Fe2Cu(ox)818- showed that both chelating and tetradentate bridging oxalate ligands were present. For Fe2Cu(ox)4(OH)4only tetradentate ligands were present.358 The IR spectrum of [ c ~ ~ ( c i t ) ~ ( H ~ Owhere ) ~ ] ~ cit - , = citrate, was consistent with the presence of unidentate c a r b ~ x y l a t e sThe . ~ ~IR ~ spectrum of (67),where S = MeOH/EtOH, R = (68), included bands due to bidentate organocarbonate (1560, 1400, 1360, 1085 ~ m - l ) . ~The ~ ' IR spectrum of solid Rh2(form)2(pyrid0[2,3-b]pyrazine)2(0~CCF~)~, form = N,N'-di-p-tolylform-amidinate anion, has vaSCO2of the trifluroacetato ligand agreeing with unidentate c~ordination.~~' Surface-enhanced IR data for methanol oxidation at a platinum electrode gave evidence for the formation of a surface formato complex (band at 1320 The complex (69), where R = CH2C02H, shows C02 modes from both unidentate and uncomplexed c a r b ~ x y l a t e sThe . ~ ~bridging ~ acetate ligands in (70) have vaSCO2at 1578 cm-' and v,C02 at 1422 C M - ' . ~ ~ ~ There have been several reports giving detailed assignments to chelating oxalate ligand modes in platinum(I1) and (IV) complexe~.~"-~ The IR spectra of ~is-Pt(L)~x, where L = hepta-methyleneimine, X = a range of dicarboxylates, including oxalate, malonate and substituted malonates, are all consistent with bidentate ligands, via two unidentate carb~xylates.~~' The unidentate trifluoroacetate ligand in [Cu(L)(F3CC02)ln,where L = Schiff base from pyridine 2-carboxaldehyde and anthranilic The IR and Raman = 9,10-dihydro-9-oxo-10-acrispectra of C U ( C M A ) ~ ( H I ~ ) ~ .where ~ H ~ OCMA , dine-acetate ion, HIm = imidazole, show that CMA is coordinated via unidentate carboxylate groups (~asCO21608 cm- v,C02 1381 ~ m - ' ) . ~vC02 ~ ' bands in the IR spectrum of [C~~(btec)(H20)~.2H20]., where H4btec = 1,2,4,5-benzenetet' 9

4: Vibrational Spectra of Some Co-ordinated Ligands

143

n

racarboxylic acid, show the presence of both uni- and bidentate carb~xylates.~~' Values for Y C O modes ~ in [Cu2(Mal)(en)212+, where H2Mal = malonic acid, and related complexes are all consistent with bidentate carboxylato coordinaSimilar data for C~~(pheida)~(AdeH)~(H~O)~, where pheida = N phenylethyliminodiacetato, AdeH = adenine, are consistent with bridging carboxylato The IR spectrum of cyclo-[tetrakis(pq3-hydroxyethanoato-l~0:2~~O',O")tetrakis( 1,lO-phenanthro1ine)tetracopperltetranitrate includes vCO2 bands of bridging carboxylate at 1576 cm-' (Yas) and 1431 cm-I (Y,) .3 74

The complexes (R'3P)-Ag-OC(O)R, where R = CF3, C2F5; R' = "Bu, C6H4CH2NMe2-2, all have IR bands confirming that the carboxylate is unidentate?75The complex [Zn2L(pl,1-HC02)-(pl,3-HC02)]22+, where L = 2,6-bis(N-2(2'-pyridylethyl)formimidoyl)-4-methylphenol, shows IR bands (vC02)confirming that there are two different coordination modes for the formato l i g a n d ~ . ~ ~ ~ The complex Gd2(p2-OOCFc)2(00CFc)4(MeOH)2(H20)2, where Fc = ferrocenyl, has Yas at 1522 cm-I, Y, at 1470 cm-' for COO-, showing bidentate carboxylato coordination.377Complexation of furoic acid (C4H30COOH,HL) to thorium(1V)was followed by studying the Raman spectrum in the range 1300 - 1800 cm-'. The data were consistent with the formation of simple complexes ThLi4-")+only.378

Spectroscopic Properties of Inorganic and Organometallic Compounds

144

DRIFT data gave assignments to C02 modes for C 0 2 coordinated to aValues of vCO2 modes showed unidentate coordination of the citrate (cit") carboxylate groups in [A12(cit)(H~it)2]~-.~'~ The IR spectra of gallium(III)/acetate aqueous solutions gave evidence for the formation of Ga(OAc)2 and Ga2(0H)2(0Ac)3 species, with the latter containing bridging acetate, i.e. [Ga2(p-OH)2(p-OAc)]3 .381 A1203.379

+

+

+

The IR and Raman spectra of (71) included the following assignments: va,N=N 1445 cm-', v C = C 1600 cm-', v,,C=O 1636 cm-', v,C=O 1329 ~m-'.~ The ' ~ IR spectra of R3Sn(L),where R = Bu or Ph, L = (72), R' = H, Me, H, C1, Me, R3 = H, Me, all included v C 0 2 bands characteristic of R2 unidentate coordination.383The IR spectra for R3Sn(L),where R = Me, "Bu, Ph; HL = 6-[d-(-)-~-amino-p-hydroxyphenylacetamido]penicillinand related, show bidentate coordination of the ligands via ester carboxylate and p-lactam ~arbonyl.~'~

+

7.3 Keto-, Alkoxy-, Ether and Related Complexes.- Ligand mode assignments were made for M ( a ~ a c )where ~, M = Ti, V, Mn or Co, based on IR spectra and DFT calculations.3s5 The IR spectrum of (CH3)20.C13V0 in an argon matrix at 14 K included vS0C2 of M e 2 0at 891 cm-', compared to 925 cm-' for the free molecule.386 It has proved to be possible to interpret the YCHmodes of the C H 3 0 radical on a W(110) surface in terms of Fermi resonance between C-H stretching fundamentals and C-H deformation overtones and combination^.^'^ Raman spectroscopy shows coordination of D M F via the oxygen atom in [Hg{(yP(C6F5)2)W(C0)5)2].2DMF, i.e. YC = 0 is at 1659 cm-', a decrease of approximately 50 cm-I from the value in free DMF.388 The Raman spectrum of Mn2+in DMF/1,1,3,3-tetramethylurea (TMU) solutions gave evidence for solvent molecule coordination (involving oxygen atoms of both D M F and TMU).389There is FTIR evidence for coordination of FeC13by

4: Vibrational Spectra of Some Co-ordinated Ligands

145

D M F in DMF solutions, thus, YC= 0 shifts from 1655 cm-I (free)to 1645 cm-' (complex).390 The supported dinuclear nickel methoxide species Ni2(OMe)2/Si02gives IR bands due to bis-p-OMe bridging units.391 The IR spectrum of U02(N03)2(NCP)2, where NCP = N-cyclohexyl-2-pyrrolidone, has YC= 0 76 cm-I lower than in free NCP, i.e. there is strong U t O = C coordination. The bidentate bridging nitrato groups gave the expected

The IR spectra of (73),where M = B, X = Cl; M = Al, X = Br; M = Ga, X = C1, Br or I, all include Y C = O of the 9-fluorenone in the range 1603 - 1652 cm-l .393 Ab initio and DFT calculations of the vibrational wavenumbers for Al(a~ac)~ enabled more detailed assignments of observed ligand modes to be made than hitherto.394The IR spectra of aluminium(II1) complexes of theaflavin ( = HL) provided evidence for AIL, AIL2, AIL3, AlL3H-I and AlL3H-2,with coordination via tropolone C = 0 and deprotonated hydroxyl FT Raman spectra were used to characterise the complexes of A13+with isoquercitin (HIso), A1(Iso)2+,Al(Iso)2+ and A1@0)3+. These also involved coordination through C = 0 and deprotonated O-H.396 7.4 Ligands Containing 0-N, 0 - P or 0 - A s Bonds. - The IR spectrum of Mg(~hen)3(NO~)~ contained bands suggesting covalent bonding of nitrate groups to the IR spectroscopy was used to study DNA complexation with Ca2+ - binding was shown to occur from the shifting and splitting of the v,,P02 band of the backbone .398 Matrix-isolation IR of the products of reaction of ovc13 and CrC1202with PH3 gave evidence for formation of PH30, and its coordination to VC13 or CrC120fragments (YP= 0 about 110 cm-' lower than in free PH30).399 Characteristic IR and Raman bands were seen from HP032- in [M(HPO3)F3I2-,where M = V or Cr, e.g. for M = V, vSPO3gave an IR band at 1025 cm-l and one in the Raman spectrum at 920 The IR spectra of M O ~ ( ~ . ~ - C ~ ) ~where ( ~ P R ~=)Et ~ or C ~"Pr, ~ ,include Y P= 0 bands at 1101 cm-' (Et) or 1086 cm-' ("Pr) - consistent with M o + O = P coordination.4°1 FTIR data showed that N O + NO2 adsorbed on to Pt-Zr02/A1203catalysts produced surface nitrato species.402Surface nitrato species were also found on N 0 / 0 2 adsorption on C U S O ~ / Z ~ O ~ . ~ ~ ~

146

Spectroscopic Properties of Inorganic and Organometallic Compounds

The IR spectra of CuL2X2, where L = p-methylacetophenone semicarbazone and related ligands, = NO3 or (S04), show that the nitrato and sulfato groups are unidentate!04 The complex AgN03.tz2(CH2),where tz2(CH2) = bis(1,2,4triazol- 1-yl)alkene,gives IR bands showing unidentate (or possibly very unsymmetrical bidentate) nitrat0.4'~ IR data for (74),where Ln = La or Pr, include bands due to q2-chelatingNO3l i g a n d ~ . ~The ' ~ IR spectrum of [Sc(Me3As0)6l3+has three strong bands in the range 840 - 925 cm-', assigned as vAsO pCH3 m0des.4'~IR bands due to Y P = O in [Ln(Me3P0)6I3+,where Ln = all lanthanides except Pm, are seen in the range 1103 - 1134 cm-', showing Lv+O = P coordination!'* Similar data were also obtained for Ln(N03)(HL)3,where Ln = La-Yb, not Pm, HL = PhC(0)N(H)P(O)(NEt2)2!09

+

I

H

The IR spectrum of SnMe2(PLP-2H),where PLP = (79, contains bands due to PO3 stretches which show that this group is coordinated to the tin 7.5 Ligands Containing 0 - S or 0-Te Bonds. - The complex facRh(C0)3(S03F)3has IR bands from the S03F ligand which are consistent with unidentate (-OS02F)c~ordination.~" The IR spectra of HS04- or S042- adsorbed on palladium single-crystal electrodes (at a variety of flat and stepped surfaces) all give a single YSOband near 1200 cm-1.412The IR spectrum of Pd(OS02)(terpy*),where terpy* = 4,4',4"tris(tert-buty1)-2,2':6',2''-terpyridine,has bands from unidentate sulfito: 1260 cm-' (YasS = 0);1133 cm-' (v,S = 0)and 983 cm-' (YS-O)."~~ The IR and Raman spectra of mercury(I1) chlorosaccharinate give bands which can be assigned to vC0, v,,S02 and vSSO2,consistent with covalent Hg(11)-saccharinintera~tion.4~ The IR spectrum of UTe04 gave the following assignments: v,Te-O(eq) 818 cm-l, v,,Te-O(eq) 749 cm-', v,,Te-O(ax) 649 cm-' and v,Te-O(ax) 561 The bridging Te205groups in [UO2(Te2O5)(OH)'],gave the following IR bands: vTeO 803,776,669,639 cm-l; 6Te0 471,446,406 cm-'.416

4: Vibrational Spectra of Some Co-ordinated Ligands

147

The Raman spectrum of aqueous Ga2(S04)3includes a band at 1002 cm-' which was assigned as a feature of the unidentate sulfato complex [Ga(OH2)50S03]+.4'7 7.6 Ligands Containing 0-C1 or 0 - 1 Bonds. - The FTIR spectra of LiC104 in propylene carbonate (PC), diethyl carbonate (DEC) or PC/DEC mixtures show that there is a strong interaction of Li+ with the solvent mo1ecules.418 The IR and Raman spectra of NaC103 in D M F solution gave data on the Na+C103- contact ion pair, with effective C, symmetry for the c103-: (a') 958, 926,610 and 480 cm-'; (a") 1003 and 497 ~ m - ' . ~ ' ~ Characteristic perchlorate ligand bands were seen for bridging, bidentate ClO4- in Re03(C104)C1206 and Sb2C16(0)(OH)(C104).420 The bridging iodate ligands (i.e. bridging two uranium atoms) in the complex with the empirical formula [U02(103)2(Cr04)]2f give Y I - 0 bands at 815, 798, 775,742,730 and 699 ~ m - ' . ~ ~ '

8

Sulfur and Selenium Donors

The IR and Raman spectra of [{Ta(Se2)2(Se)}2Se]4include vSeSe bands of the y2-Se2ligands at 247,236 and 215 ~ r n - ' . ~ ~ ~ The complex (76) gives IR bands at 1518 cm-' (YCN)and 1076 cm-' (YCS) characteristic of the q2-S2CNEtzligand.423Assignments to analogous modes were made from the IR spectra of MoO,(Rdtc),, where Rdtc- = 2-, 3- or 4-methylpiperidinodithio~arboxylates.4~~Values for YNO in the complexes (Tp*)Mo(NO)(S-S), where S-S = range of ene- 1,2-dithiolate ligands, Tp* = hydro-tris(3,5-dimethyl-1-pyrazolyl)borate,show a good correlation with the electronic properties of the S-S ligand.425 The complex (77) has IR bands due to the C = CE2 fragment as follows: M = Mo, E = Se, 1405,1375,888 cm-'; M = W, E = S, 1400,1374,889 cm-'.426An IR band due to Y C = O of the dithiocarbonato ligand in C ~ M O M ~ ( C O ) ~ [ ~ SC( = O)S] was observed at 1741 cm-'.427 For the complex (78), YS= 0 is at 1119 cm-' and vSi-0-Si at 835 cm-'."28The IR spectra of (79), where R = Me or Et, both include a Y C = O band (from the benzoyl group) near 1685 For (80) and related species, YCN bands were seen for ql- (near 1550 cm-') and y2- dithiocarbamato (near 1460 cm-') l i g a n d ~ . The ~ ~ ' complex (81), where X = S02Ph, has vSO2 IR bands at 1309 and 1146 ~ m - ' . ~ ~ ' IR and Raman spectra were reported and PS4 modes assigned for the Nips4chains in (PPh3-X-PPh3)o,5[NiPS4], where X = C2H2 or C3H6.432The complexes c ~ ~ - M ( ~ , ~ , ~ , ~ - S C ~ Hwhere F ~ ) ~M( L=- LNi, ) , Pd or Pt, L-L = dppm or dppe, have an IR band at 910 - 915 cm-', characteristic of the S-bound tetrafluorothiolate l i g a n d ~The . ~ ~IR ~ spectra of M(HL)2,where M = Pd or Pt, H2L = N,N'-bis(carboxymethyl)ethanedithioamide,are consistent with square planar geometry and S,S-bidentate ligand ~oordination.4~~

148

Spectroscopic Properties of Inorganic and Organometallic Compounds

(78)

0

+

+

The complex [(TMPA)CU-S-S-CU-(TMPA)]~+ - the first example of a copper complex with an end-on bridging disulfide ligand - has a resonance Raman band at 499 cm-' due to Y S S (shifting to 490 cm-' for 34S).435 The side-on p-q2:q2bridged Cu2(S2) complex [Cu"{ HB(3,5-iPr2p~)3)]2(Sz) gives a similar band at 500 cm-l (32S), 488 cm-' (34S).436 The IR spectra of Ag(tu),N03, where n = 1- 4, have YC= S bands showing the presence of both terminal (724 cm-') and bridging (698 cm-l) thiourea ligands (except for n = 1, which only contains bridging l i g a n d ~ ) . The ' ~ ~ adsorption of 1,4-dithiane on a gold monolayer gives SERS data consistent with both gauche and trans forms at the ~ u r f a c e . 4 ~ ~

f7

"T"

"

R2

Se

The complex Au(LtBu)2, where H2(LtB")= 3,5-di-tert-butyl-l,2-benzenethiol, gives an IR band due to v(C=S*) of the S,S-coordinated o-dithiobenzosemiquinonate(1-) radi~als.4~' The IR spectra of (L)AuCN, where L = (82), R

4: Vibrational Spectra of Some Co-ordinated Ligands

149

= R' = H; R = H, R' = Me, Et, 'Pr or Ph, show that for R = R' = H the monomer exists. For the other cases the complexes must be formulated as [AuL~] [ A u ( C N ) ~ ] - . ~ ~ +

9

Potentially Ambident Ligands

9.1 Cyanates, Thio- and Selenocyanates and their Iso-analogues. - The IR and Raman spectra have been reported for Sr(I1) and Ba(T1) ion-pairs with thiocyanate in liquid ammonia. There was evidence for [M2+-NCS-] +,SCN--M2+NCS-, and a solvent-separated ion-pair, [(H3N),M2+-NH3-NCS-] .441 There is IR evidence for the formation of Ti-NCO (2205 - 2210 cm-') and Au-NCO (2180 - 2190 cm-') as a result of the NO + CO reaction on Au/Ti02 catalysts.442TRIR data (YasNCS) at 77 K were used to probe the L+M C.T. excited states for Cp2Ti'V(NCS)2.443 The IR spectra of [CuL,] [Cr(NCS)6]2.mH20,where L = 1-methylimidazole and related ligands, all contain bands from NCS- groups bridging Cr(II1) and [Mn(salpn)-NCSI2, where H2salpn = N,N'-bis(salicy1idene)C U ( I I ) .Dimeric ~~ 1,3-diaminopropane, has v,,NCS at 2043 cm-' from N-bound NCS. The polymeric analogue has this mode at 2068 cm-', from end-to-end bridging l i g a n d ~ . ~ ~ IR and Raman spectra have been reported for high-spin and low-spin forms of Fe(~hen)~(NcS and ) ~ ,assigned with the aid of DFT calculations. It was suggested that the LS state had C2, the HS C1 symmetry.446Tran~-Fe(BPM)2(Ncs)~, where BPM = tris(1-pyrazolyl)methane, has YCN at 2075/2064 cm-', vCS 769 cm-' and 6NCS 480 cm-1.447The IR spectrum of Fe(L1SQ)2(NCS), where (LISQ).= mradical anion N-phenyl-o-imino(4,6-di-tert-butyl)benzosemi-quinonate, has YaSNCS at 2050 cm-' from N-coordinated NCS-.448 Characteristic NCS bands were seen, consistent with M-NCS coordination, in the IR spectra of trans- and cis-[Co(NCS)2(tmd)]+, where tmd = tetramethylethylenediamine."49 IR and Raman spectra (with DFT calculations) gave assignments to S-bound SCN- modes and oxalate (bidentate chelate) ligand modes for [Pt"( SCN)2(~~)]2and [Pt1v(SCN)4(ox)]2-."50 The IR spectrum of polymeric C U ( ~ ~ ) ~ [ C ~ ( S C gave N)~ evidence ]~ for the presence of both 1,l-p-SCN and 1,3-p-SCN bridging +

9.2 Ligands Containing N and 0, N and P or P and 0 Donor Atoms. - The FTIR spectra of M2+-theophyllinecomplexes (M = Mg or Ca) show coordination via carbony10 and N7 atoms (Ca) or N7 alone (Mg).452 The TR spectra of [Zr(OH)2L]C12,where L = semicarbazones derived from 4-amino-antipyrine and various aryl aldehydes, all show IR bands consistent with N,N,O-c~ordination."~~ The IR spectra of v(o)(so,) complexes with cyclobutane-, cyclopentane- and cycloheptane-carboxylic acid hydrazides all show coordination to vanadium via carboxyl0 and primary amino N.454IR spectra of complexes of 4-amino-N-(5methyl-3-isoxazolyl)-benzene sulfonamide (SMZ) with VO(II), Co(II), Ag(I), Cd(II), Hg(I1) and U02(II), show that in the VO(I1) and Ag(1) complexes the

150

Spectroscopic Properties of Inorganic and Organometallic Compounds

ligand is unidentate via sulfonamide 0, in the Co(I1) and Cd(II) complexes it is bidentate via N of NH2 and 0 of S02NH, while in the Hg(I1) and U02(II) complexes it is bidentate via 0 and N of S02NH.455 Complexes of Mo, W and Re with H2(nicO) (nicotinic acid), e.g. [ M 0 ~ 0 ~ ( H n i c O ) show ~ ] ~ - coordination via both N and 0 atoms. For Pd and Pt, e.g. P d c l ( H n i ~ O ) ( P P h ~ coordination )~, only occurs via N.456 YC= 0 for (83) is seen at 1678 cm-' (R = H) or 1674 cm-' (Me), showing that the carbonyl group is not coordinated. (84), on the other hand, has Y C = O at 1514 cm-' (R = H), 1516 cm-' (Me) (here YC= 0 is coupled with YC= C).457 R

R

Ph

Ph

(83)

0

(84)

The IR spectra of M(MSH)4C12,where M = Mn, Fe, Co or Ni, MSH = CH3S02NHNH2, are all consistent with coordination of MSH via the amino N atom.458The IR spectra of nicotinamide (nia) complexes M(II~~)~N~(CN),, where M = Mn, Co, Ni, Cu or Cd, and where M = Ni, Cu, C D or Hg, X = C1 or Br, show coordination only through the ring N.459 IR data for Mn3(ppi)2(p-OAc)4(H20)2, where Hppi = 2-pyridylmethyl-2-hydroxy-phenylamine, show YCH at 291 1 cm-l and YCN at 1627 cm-', consistent with coordination of imino N.460Similar measurements on [M(PZA)2Ni(CN)4]n, where M = Mn, Co, Fe, Ni and Cd, PZA = pyrazinamide, show that PZA is coordinated to M through the carbonyl 0.461 The IR spectra of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(I1) or U0 4 II) with N-(2-furylidene)benzothiazole-2-ylacetohydrazide, show that coordination either occurs as HL (viaazomethine N and carbonylo) or as L- (tridentate through enolic 0,azomethine N and furan ring O).462 The IR spectrum of (85), and related species, all have v C = O of the coordinated amidic group in the range 1500- 1530 c111-l.~~~ The complexes ReOX2(Lhis-N,N,O), where his = histidine, X = C1 or Br, have vaSC02near 1690 cm-', v,CO2 near 1373 cm-', showing unidentate coordination of the carboxylate frag~ent.4~~ IR and Raman spectra of Fe(I1) and Zn(I1) complexes of benzaldiazine and salicyldazine were consistent with C2h~ y mm etry .4 The ~ ~complex [Fe(N02)(L)]-, where L = 2,6-C6H3N-[CMe(CH2NH2)2]2, were consistent with C 2 h symmetry.466 The unstable species (86) showed YC= N at 1632 cm-l in the IR ~pectrum.4~' The IR spectrum of Ru(H~L)(DMSO)~CI~, where H2L = 2-(N-(2-hydroxyphenyl)carbamoyl)pyridine,shows that the H2L is coordinated via pyridyl N and carbonyl 0.468

4: Vibrational Spectra of Some Co-ordinated Ligands

151

The complexes [C0"'2(tpb)(CN)4]~- and related species, where H4tpb = 1,2,4,5-tetrakis(2-pyridine)carboxamido)benzene,give IR bands due to YC= 0 and v C = N in the range 1540 - 1700 cm-'.469 The IR spectra of LM(OAc)(H20)2.nH20, where M = Co, Ni or Cu, HL = 5-(2-carboxyphenylazo-2-thiohydantoin, show that L- is coordinated via azo N, carboxylate 0 and thiohydantoin 0 at0ms.4~~ The mixed-ligand complexes of Co(II), Ni(I1) and Cu(I1) with cytidine and amino-acids have IR spectra showing that the nucleoside is unidentate via N(3) only, while the amino-acids are bidentate through amino N and carboxylate 0.471

The IR spectra of Co(II), Ni(I1) and Cu(I1) complexes of 2-phenyl-3-(paminophenyl)-4-quinazolone semicarbazonesor thiosemicarbazonesshow coordination involving amine and imine N and O/S atoms of the (thio)semicarbaz0nes.4~~ Similar results were obtained for analogous complexes of substituted isoquinoloine semi- or thiosemicarba~ones.4~~ IR and Raman spectra were reported for CoL2,where HL = 2-cyano-2-diethoxythiophosphorylacetone, consistent with N,O,S-coordination by L-.474 Variable-temperature IR spectroscopy was used to follow the nitro/nitrite conversion of Ni'1(N,N'-dimethylethylenediamine)(N02)2.475 The IR spectra of Ni[(RO)2PS2]2(Ap~~), where R = Me, Et or Pr, Apsc = 2-acetylpyridine semicarbazone, show Apsc acting as a neutral bidentate ligand.476IR data for [MLI2+,where M = Ni(II), Cu(II), Zn(II), Cd(I1) and Hg(II), L = macrocyclic Schiff base, include bands showing N,O-coordination of L.477 ?

/"

C

\

I

NT32

I

2+

152

Spectroscopic Properties of Inorganic and Organometallic Compounds

Vibrational assignments have been proposed for ligand modes in (87) and (88), where M = Pd or Pt, X = C1, Br or I, LH2 = monothiomalonamide~78 Raman and IR spectra of M(L)2C12,where M = Pd or Pt, L = 0-,p- or p-dimethylphosphinylmethyleneoxyaniline, all show coordination to M via the amino Ligand mode assignments have been proposed from the IR spectra of PtCl,(L), where L = Ph2POCH2CH2NMePPh2!80The IR spectrum of Pt(HPxSC)C13, where H2PxSC = pyridoxal semicarbazone, contains bands indicating that the ligand is O,N,O-tridentate?" The IR spectrum of Cu(bhac)(Hdmpz),where Hdmpz = (89), bhac2- = (90), shows that bhac2- is coordinated through enolate 0,imine N and deprotonated 0, while Hdmpz is coordinated through imine N The IR spectra of Cu(dmdp)X, where X = C1, Br, I, NCO, N3,dmdp = dimethyldipicolinate, and C ~ ( d r n d p ) ~show + , coordination as an O,O,N-tridentate ligand!83

I

(91)

H

I

(92)

H

The complex ([C~(oxbe)]Mn(H~O)[Cu(oxbe)(DMF)]}~, where H30xbe = (91), has a IR spectrum revealing coordination by C = O groups to Mn, and N,N,O-coordination to copper."' IR spectra of CuC12(HL), AuC12(L) and [Zn(L)]+, where HL = (92),are consistent with tridentate coordination for both L- (phenolic 0 and two azomethine N atoms) and HL (phenolic 0,azomethine N and C = O).485 The IR and Raman spectra of (CU~[(E~O)~P(S)C(CN)CM~(O)~],, contain ligand bands showing coordination to one copper via 0 and S atoms, and to the other copper via CN.486 The IR spectra of Ag(ONO)(R3E), adducts, where E = P, As or Sb, x = 1 - 3, are all consistent with the presence of a nitrite ligand.487The IR spectra of (93) and related systems show that the lactam YC= 0 is shifted by about 110 cm-' to lower wavenumber than for the free ligand.488 The IR spectrum of an Hia ( = imidazole-4-acetic acid) polymeric complex, [ZnCl(ia)(Hia)],, show that ia- is acting as a bidentate bridging ligand involving N(l) and the carboxylate 0 atoms.489IR data for ZnL,, where HL = (94) and related, show coordination through two N atoms.490

4: Vibrational Spectra of Some Co-ordinated Ligands

153

The complexes M ( n b ~ ) ~ ( H ~where 0 ) , , M = Cd, n = 4;M = Hg, n = 3, nbs = benzoxasulfamate(1-),have IR spectra which show that nbs is only coordinated contains through N.491The IR spectrum of trun~-Hg[Ph~PNP(0)Ph~-P,0]~ bands confirming the P,O-c~ordination!~~ IR spectra of LnL2(N03)3, where L = diethyl-2-amino-2-oxaethylphosphonate, Ln = La, Ce, Sm, Eu, Er or Yb, show unidentate coordination through the phosphoryl IR data for ThX4Ln, where X = C1, Br, I, NCS, C104, n = 2; X = NO,, n = 1, L = 4-[N-(furfura1)aminoI-antipyrine semicarbazone and related, all show that L ligands are neutral N,N,O-donor~:~~ Adsorption of NO on KxGa,Sn8-x016 thin films gave IR bands due to both 0and N-bonded NO2l i g a n d ~ . ~ ~ ~ The IR spectra of diorganosilicon(1V)complexes of Schiff bases l-acetylferrocene thio-semicarbazone and 1-acetylferrocenesemicarbazone show that they involve Si-N and Si-0 or Si-S c~ordination!~~ IR data for [Pb(H20)(pOAc)(psac)ln, where sac- = saccharinate, show that sac- acts as a bridging ligand through N and 0 (carbonyl) 9.3 Ligands containing N and S Donor Atoms. - IR spectra have been reported and assigned for the S-bound complexes [Re111L6]3+, where L = thiourea, N-met hyl, N-eth yl or N,N-dimet h yl-t hi0urea.4~~ The IR spectra of FeL2C12, MLC12, M = Co, Ni, Pd, Zn, Cd, and ( C U C ~ ) ~ L ~ , where L = 3-N-dibenzofurylthiourea, all show N,S-coordination by L.499Similar coordination was shown for [Fe(L)2]X,where X = Cl, c104, N03, L = (95).50" The complex [Fe(MPzNPr&]+, where HMPzNPr, = 5-methyl-3-formylpyrazole-N(4)-dipropyl thiosemicarbazone gives IR bands from the strongly N,N,S-coordinated ligand.501 The IR spectra of RuC12(q4-CgH12)Land MC12L, where M = Pd, Pt, L = S-acetyl-NP-acetyl-dithiocarbazate and related, all contain bands showing bonding involving thio-oxo S and carbazate NP.502 H

n

H \

C=N-N-

/

H

R

c-N

x

I.

I

H

(95)

H

I R data for [Co(L),]+ and [Ni(HL),I2+, where HL = (96), R = CH2CH2CH2CH3, reveal that L- is coordinated via pyrazolyl N, azomethine N

154

Spectroscopic Properties of Inorganic and Organometallic Compounds

and thiolato S, while HL is tridentate via pyrazoliminic N, azomethine N and thioketo S.503Thiourea ligand mode assignments were made for [M(TU)6]2+, where M = Co(II), Ni(I1) and Cu(I1) - all were consistent with M-S coordinati~n.~@' The IR spectra of Ni(II), Cu(IT),Cd(I1) and Zn(I1) complexes with Schiff bases from benzyl dithiocarbazate and 5-methyl-2-furaldehyde or 2-furyl-methylketone, gave ligand mode assignments showing thiol S and azomethine N c~ordination.~'~ The IR spectra of thionicotinamde complexes of Pd(II), Pt(II), Zn(II), Cd(I1) and Hg(I1) are all consistent with S,N-coordination to the met SERS measurements of 4-mercaptopyridine on silver surfaces show the formation of an Ag-S bond.507 Raman and IR spectra of Zn(ISTSC)2and Hg(ISTSCH)Br2,where ISTSCH = isatin-2-thiosemicarbazone, suggest N,S-coordination to Zn, and S-coordination to Hg."' IR data for Hg(HAm4DM)X2, where HAm4DM = 2-pyridine formamide-N(4)-dimethylthiosemicarbazone,X = Cl, Br or I, all show coordination via S and two N (py, azomethine) atoms.509 The IR spectrum of (TlMe2)2(DAPTSC).where H2DAPTSC = 2,6-diacetylpyridinebis(thi0-semicarbazone),shows coordination via N(2),S(l)/N(6),S(2)to two thallium Similar data for Me2Sn(Me2Pymt)2,where HMe2Pymt = 4,6-dimethylpyrimidine-2-thioneand related, all show N,S-chelation by the ligand.5'1 9.4 Ligands Containing S and 0 Donor Atoms. - IR ligand mode assignments for BaCr2(bipy)2( 1,2-dto~)~(H20)2, where dtox = dithio-oxalato, are consistent with S-c~ordination.~'~ The complex trans-[Ru(NH3)4(SO2)C1]+ has vSS02at 1110 cm-', ~ $ 3 0 1257 2 cm-', from q'-S-bound SO2. Photolysis of this converts it to a metastable q2-side-bound SO2 complex (Y,SO~943 cm-', ~ 3 0 1167 2 ~ m - ' ) . ~Cis, ' ~ cis, cis-RuC12(dmso-S)2(dmso-O)(CO) has YSObands at 1114 cm-' (dmso-S) and 916 cm-' (dms0-0).~'~ The S-bonded dmso in [ M " ( d m ~ o ) ~ M o ~ O ~where ~ ] ~ -M , = Ru or Os, gives YSObands near 1105,1022 and 1010 ~ r n - ' . ~ ' ~ The IR spectrum of C~~(2-MeSmic)~(dmso)~, where 2-MeSmic = 2-methylthionicotinate, includes vS = 0 at 956 cm-', i.e. the dmso is O-co~rdinated.~'~ The complexes S~(pic)~(L)~, where pic = picrate, L = dmso, tetramethylene sulfoxide or 1,3-dithiane-l-oxide, all have IR bands due to v S 0 showing 0c~ordination.~" The IR spectra of Ln(~ic)~.2.5(BsMB), where Ln = La, Ce, Nd, Sm, Eu, Tb or Er; BSMB = o-(benzylsulfury1)methyl benzoate, show coordination of BSMB via the SO group. In addition, the picrate was shown to be bidentate, involving phenolic and o-nitro group 0 atoms.518IR data for Ln(N03),(dtso),,where Ln = Nd - Lu, Y; dtso = (97), show Ln-0 coordination by both dtso and N03.'19

4: Vibrational Spectra of Some Co-ordinated Ligands

155

The complexes U02(NO&(L), where L = diphenyl- (vS0 936 cm-') or dibenzyl- (941 cm-') sulfoxide, both have U - 0 coordination (bands were also seen in the IR spectra due to bidentate nitrato Raman and IR spectra gave typical ligand modes for qi-0-coordinated dmso in [ M ( d m ~ o ) ~ ] ~ where +, M = Al, Ga or In.521 The complex Ph2Pb[(OPPh2)(SPPh2)NI2had IR bands at 1240 cm-' (vasP2N),1040 cm-' (vP0) and 570 cm-' ( Y P S ) . ~ ~ ~

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4: Vibrational Spectra of Some Co-ordinated Ligands

415. 416. 417. 418. 419. 420. 421. 422. 423. 424. 425. 426. 427. 428. 429. 430. 431. 432. 433. 434. 435. 436. 437. 438. 439. 440. 441. 442. 443. 444. 445. 446. 447. 448.

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170 449. 450. 451. 452. 453. 454. 455. 456. 457 458. 459. 460. 461. 462. 463. 464. 465. 466. 467. 468. 469. 470. 471. 412. 473. 474. 475. 476. 477. 478. 479. 480. 481.

Spectroscopic Properties of Inorganic and Organometallic Compounds

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482. S. Das, G. P. Muthukumaragopal, S. Pal and S. Pal, New J . Chem., 2003,27,1102. 483. M. A. S. Goher, F. A. Mautner, A. K. Hafez and A. A. Youssef, Polyhedron, 2003,22, 515. 484. S.-Q. Zang, R.-J. Tao, Q.-L. Wang, N.-H. Hu, Y.-X. Cheng, J.-Y. Niu and D.-Z. Liao, Inorg. Chem., 2003,42, 761. 485. F. Ueso-Urena, N. A. Illan-Cabeza, M. Moreno-Carretero, J. M. Martinez-Martos and M. J. Ramirez-Exposito, J . Inorg. Biochem., 2003,94,326. 486. Z. A. Starikova, A. G. Mateeva and M. P. Pasechnik, Zhur. Neorg. Khim., 2002,47, 1793. 487. A. Cingolani, Effendy, M. Pellei, C. Pettinari, C. Santini, B. W. Skelton and A. H. White, Inorg. Chem., 2002,41,6633. 488. M. Limmert, I.-P. Lorenz, J. Neubauer, A. Schulz and H. Piotrowski, Z . anorg. allg. Chem., 2003,629,223. 489. P. Drozdiewski, B. Pawlak and T. Gkowiak, Polyhedron, 2002,21,2819. 490. B. Marias, I. Garcia, M. V. Villa, J. Borras, A. Castifieiras and F. Sanz, Z . anorg. allg. Chem., 2003,629,255. 491. V. T. Yilmaz, T. K. Yazicilar, 0. Andac, H. Kutuk, Y. Bekdemir and W. T. A. Harrison, Z . anorg. allg. Chem., 2002,628, 1908. 492. R. Haid, R. Gutmann, C. Czermak, C. Langes, W. Oberhauser, H. Kopacka, K.-H. Ongania and P. Bruggeller, Inorg. Chem. Cornrn.,2003,6,61. 493. J. Petrova, S. Momchilova, N. G. Vassilev and E. T. K. Haupt, Heteroatom Chem., 2003,14, 128. 494. R. K. Agarwal, N. K. Sharma and I. Chakraborti, J . Saudi Chem. Soc., 2002,6,41. 495. K. Fujimoto, J. Suzuki, M. Harada, S. Awatsu, T. Mori and M. Watanabe, Res. Chern. Intermed., 2002,28,493. 496. R. V. Singh, M. Jain and P. Nagpal, Main Group Metal Chem., 2002,25,615. 497. V. T. Yilmaz, S. Hamamci, 0.Andac and K. Guven, Z . anorg. allg. Chem., 2003,629, 172. 498. D. Gambino, E. Kremer and E. J. Baran, Spectrochim. Acta, 2002,58A, 3085. 499. A. Kriza, A. Reiss and N. Stanica, Rev. Roum. Chim., 2001,46,503. 500. N. C. Saha, R. J. Butcher, S. Chaudhuri and N. Saha, Polyhedron, 2003,22,375. 501. N. C. Saha, R. J. Butcher, S. Chaudhuri and N. Saha, Inorg. Chim. Acta, 2002,339, 348. 502. B. N. Shailendra, F. Naqui and A. Azam, Helv. Chim. Acta, 2002,85,2713. 503. N. C. Saha, R. J. Butcher, S. Chaudhuri and N. Saha, Polyhedron, 2003,22,383. 504. G. M. S. El-Bahy, B. A. El-Sayed and A. A. Shabana, Vib. Spectrosc., 2003,31,101. 505. M. T. H. Tarafder, K. T. Jin, K. A. Crouse, A. M. Ali, B. M. Yamin and H.-K. Fun, Polyhedron, 2002,21,2547. 506. A. Reiss, V. Muresan, N. Muresan and A. Danet, Analete Univ. Craiova, Ser. Chim., 2000,29,79 (Chem. Abs., 2002,137,303748). 507. J. Hu, B. Zhao, W. Xu, B. Li and Y. Fan, Spectrochim. Acta, 2002,58A, 2827. 508. N. T. Akinchan, P. Droidiewski and W. Holzer, J . Mol. Struct., 2002,641,17. 509. E. Bermejo, A. Castifieiras, I. Garcia and D. X. West, Polyhedron, 2003,22,1147. 510. J. S. Casas, E. E. Castellano, J. Ellena, M. S. Garcia-Tasende, A. Sanchez, J. Sordo, E. M. Vazquez-Lopez and M. J. Vidarte, Z . anorg. allg. Chem., 2003,629,261. 51 1. R. M. Fernandes, E. S. Lang, E. M. V. Ezequiel and G. F. de Sousa, PoEyhedron, 2002,21,1149. 512. U. Heinl, U. Kleinitz and R. Mattes, Z . anorg. allg. Chem., 2002,628,2409. 513. A. Y. Kovalevsky, K. A. Bagley, J. M. Cole and P. Coppens, Inorg. Chem., 2003,42, 140.

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5 Gas-phase Molecular Structures Determined by Electron Diffraction BY D.W.H. RANKIN AND H.E. ROBERTSON

1

Introduction

Over the many years that we have been writing reviews of inorganic structures determined by gas electron diffraction, we have observed with interest how the subject has changed. On one hand there has been a dramatic and continuing improvement in the technical quality of the research, largely but not entirely driven by the development of computational power. On the other, the volume of results has been remarkably stable, with about 40 to 50 papers being reviewed each year. The complexity of the subjects of these studies has certainly increased, and determination of structures of relatively large molecules is probably now one of the most important roles for the technique. But a year ago there was a step change. The number of papers to be reviewed dropped by nearly a half. Was this just a random fluctuation, or an intimation of a permanent change? We decided not to contribute a review in 2003, but to combine the output of two years in a single chapter in 2004. That we have now done, and there are only just over 50 references altogether. It seems that there is indeed a significant decline in the number of publications, which is likely to continue in the near future. Gas electron diffraction continues to be a powerful and important tool, capable of tackling large and complex molecules with impressive accuracy. The combination of theory and experiment has made enormous strides, with one technique, the SARACEN method, the subject of an extensive review.' We have been impressed by the many instances of structures, particularly inorganic, that do not conform to our expectations, and by the still substantial areas where theory does not reproduce experimental results. There is, and will continue to be, significant demand for gas electron diffraction for years to come. Unfortunately, the number of practitioners is set to decline further, with the action increasingly focussed in Russia. As usual we present geometrical parameters of the structural type (re,ra, rg,Y,, etc.) reported in the original papers and with the same uncertainties, quoted in parentheses after numerical values. Spectroscopic Properties of Inorganic and Organometallic Compounds, Volume 37 0The Royal Society of Chemistry, 2005 173

174

Spectroscopic Properties of Inorganic and Organometallic Compounds

The following compounds are included in this report. Section 2, Group 12: ZnMe2, Zn(CH2SiMe3)2,ZnEt2, ZnPrn2,Zn(ne~-Pe)~, ZnPri2,ZnBu'2, Zn(C5H5)2. Section 3, Group 13: B2F4, B4F&O, (CF&BCO, B(OCH2CH2)3N (boratrane), Me3GaNHEt2, H3GaPMe3. Section 4, Group 14: CHI3, perfluoro-bicyclo-[2,2,O]-hex-1(4)-ene,C20C110 (decachlorocorannulene), SiH212, trans-Cl(SiH3)C=C(SiH3)CI, Br(SiH3)C=CH2, C6H5SiH3,1,2-C6H4(SiH3)2, 1,3-C6H@iH3)2, 1,4-C6H4(SiH3)2, 1,1-(Me3SiC=C)2cyclopropane, SiH3CH2CH2CH3,CH3SiH2CH2CH3,(HC=C)2-silacyclobutane, 1,4-disilacyclohexa-2,5-diene, 1-Me-1-silacyclohexane. Section 5, Group 15: (CF3)2NON02, CF3N(0)NF, 1,2-CsH4F(N02), HC(S)NMe2, C1C(S)NMe2, PH2Ph, PHPh2, P(OCH3)3, P B u ~ ( S ~ C ~ ~ ) ~ , C6H4(NMe),PC1,Me4PF, (Me2P(=O)OH),. Section 6, Group 16: CF300C(0)F,CF30C(0)OOC(O)CF3,CH30C(O)SCl, CF3C(O)N=SF2, CF3C(O)N=SF(CF,), FC(O)N=SCl2, CF30S02C1, S(NBu')2, S(NBu')3. Section 7, Transition metals, lanthanides and actinides: Cu2CI2, Cu3C13, Cu4C14,Nd12,NdBr3,YC13,Y2C16,NbOBr3, NbSBr3,NbOC13, S~(acac)~, Sc(dpm), (dpm = ButCOCHCOBut), L a ( d ~ m ) ~ ,E r ( d ~ m ) ~ ,Cu(1,5-cod)(hfac), Ru(GMe5)(GF5),C2H5Re03, Zr(BH4)4, U(BH4)4. 2

Compounds of Elements in Group 12

Two papers describe structures of organozinc compounds. Seven dialkyl zinc compounds have been studied by Density Functional Theory (DFT) at the B3LYP/SDD level, and new GED data are reported for the iso-propyl, tertbutyl, neo-pentyl and trimethylsilylmethyl derivatives? Structures had been described earlier for the methyl, ethyl and n-propyl compounds. Both the experimental and the theoretical Zn-C distances increase in the order ZnMe2 w Zn(CH2SiMe3)2< ZnEt2 w ZnPrn2z Zn(neo-Pe)z < ZnPri2< ZnBut2,with the relative values closely matched by bond rupture enthalpies. The new Zn-C bond lengths are 196.1(3)pm (R = Pri), 197.4 pm (R = But), 196.0(3)pm (R = neo-Pe) and 193.5(6) pm (R = CH2SiMe3).These correlate with the inductive Taft constant, so variations in bond lengths are largely determined by the electronwithdrawing power of the alkyl groups. In the case of di-cyclo-pentadienylzinc it is not simply the Zn-C bond lengths that are of interest, but the mode of coordination of the l i g a n d ~Three . ~ possibilities have been considered, q5,q5,q3,q3and q5,q1.DFT calculations at the B3LYP/LanL2DZ level indicated that the q5,q1(slipped sandwich, C , symmetry) option had the lowest energy, 16.2 kJ mol-I below a two-dimensional saddle point of DSdsymmetry, and 2.8 kJ mo1-' below a saddle point with C 2 h symmetry, corresponding to an q3,q3structure. Analysis of the GED data gave an R factor of 0.174 for the DSdstructure, 0.078 for C2h,and 0.047 for C,, so the q5,q'option is clearly favoured. (It also complies with the 18-electron rule.) For the 9'ring the shortest Zn-C distance is 210(3) pm, and the angle between the centre of gravity

5: Gas-phase Molecular Structures Determined by Electron Difraction

175

of the five ring carbon atoms, this carbon atom and zinc refined to 95(4)". The fact that this angle is so much smaller than expected for an sp3-hybridisedatom is used to justify the description of the molecule as having a slipped-sandwich structure. For the q5ring the Zn-C distances are 217(6), 223(3) and 233(4) pm, so the zinc atom is not perfectly centred above the ring. The ring centre of gravityZn-C(q' ring) angle refined to 187(6)".

3

Compounds of Elements in Group 13

The equilibrium geometry of diboron tetrafluoride has been obtained by reanalysis of data obtained at temperatures between 193 and 420 K.4calculations were performed using a variety of methods, HF, MP2, CCSD and B3LYP, with basis sets including cc-pVDZ, aug-cc-pVDZ and cc-pVTZ, as well as Gaussian sets up to 6-31 1+G*. The energy difference between planar ( D 2 h ) and twisted (D2J forms was never more than about 2 kJ m o P , but there was no consistent pattern, although the planar conformation was preferred more often than the twisted one. The refined structure was based on simultaneous fitting of geometrical and force-field parameters to GED data and vibrational frequencies. The refined structure was planar, with equilibrium parameters B-B 171.9(4)and B-F 130.9(2) pm, and the angle BBF 121.1(1)". The barrier to rotation was 160(50) cm-' [0.19(6) kJ mol-'1. Structures of several borane carbonyls have been determined in the gas phase, and there are now two more to report. (BF2)3BC0is formed by reaction of CO with BXF12, and its structure in the gas phase is very similar to that in the c r y ~ t a l . ~ MP2/6-3 1l G * calculations indicate that it has C3"symmetry, and the experimental data lead to a torsion angle of just 2.0(2)O (r, structure) for the BF2groups, away from the position in which one B-F bond of each group eclipses the B-C bond. The eclipsing B-F bond is 1.5(1) pm longer than the other one, with the average distance 133.0(1)pm, and the BBF angle for these bonds is 2.6(1)" larger than the other, with the average angle 122.2(6)". The CBB angle refined to 108.3(24)",and the B-C and C-0 distances to 150.2(5) and 115.8(3)pm respectively. Tris(trifluoromethy1)borane carbonyl, (CF3)3BC0,has been prepared by solvolysis of K[B(CF3)4] in concentrated sulfuric acid, and its structure has been determined, using a combination of electron diffraction and microwave spectroscopy! The molecule has C3 symmetry, with the CF3 groups rotated 11.5(9)"(rz structure) away from the staggered positions. The B-C(carbony1) and B-C(CF3) distances refined to 161.7(12) and 163.1(4) pm respectively, while the mean C-F distance refined to 134.8(1) pm, with differences between the three individual distances fixed as calculated (MP2/cc-pVDZ level).The angle between the B-C(carbony1) and B-C(CF3) bonds was 103.8(4)", corresponding to 114.5(4)" between two bonds to CF3 groups. The B-C bond to the carbonyl group was thus 1.4 pm shorter than that to the trifluoromethyl group, whereas in the crystal it was found to be 9 pm longer. Calculations give a remarkable mix of results, with differences of 7.4 pm (longer to the carbonyl group) at the HF/6-

176

Spectroscopic Properties of Inorganic and Organometallic Compounds

311G(2d) level, -1.3 pm at MP2/cc-pVDZ and -5.7 pm at B3LYP/6-311+G*. Boratrane, B(OCH2CH&N,is one of a family of compounds in which donor and acceptor atoms are more or less forced to interact, but where there is a great deal of flexibility about the extent of that interaction. Substantial differences between structures in gaseous and solid phases of silatranes have been observed. A somewhat smaller, but still large, difference has now been reported for boratrane,7 with the B-N distance 184.6(42)pm in the gas phase (rg),compared with 167.64(7) pm in the crystal. The other gas-phase bond lengths were C-N 146.6(18),B-0 141.5(27)and C-C 150.7(27)pm, with the C-0 distance fixed at 142.2 pm. Coordination at boron is far from regular tetrahedral, with angle (<J NBO 98.7(21)",while the nitrogen atom was a little closer to regular tetrahedral, with BNC 102.0(14)". The BNCCO rings were not planar, with twist angles about the bonds of up to nearly 50". Overall the molecule had C3symmetry. There is continuing interest in potentially useful precursors for deposition of materials for electronic devices, of which 13/15 semiconductors are particularly significant. The adduct of trimethylgallium and diethylamine has been investigated as a gallium nitride precursor, without success.8In the gas phase it adopts a gauche-anti conformation, with GaNCC torsional angles of 15l(4) and -100(4)", quite close to those given by HF, B3LYP and MP2 calculations with 63 11+G(d) and 6-311G(d) basis sets. In the rg, ea structure the Ga-N and Ga-C distances were 220.4(12) and 199.6(3) pm respectively, with C-N 147.4(4) and C-C 154.4(4) pm. Refined angles were NGaC 99.5(13), GaNC 112.5(9), NCC 114.8(8), CNC 113.3(11) and CGaC 117.3(7)".Gallium-nitrogen bond lengths seem to vary rather a lot in amine complexes of trimethylgallium, from 209 pm in the trimethylamine complex to over 220 pm in the present example. The adduct of gallane with trimethylphosphine has also been studied.' In this case curvilinear atomic motions were considered, using the program SHRINK, to calculate vibrational corrections and amplitudes, giving an r h l structure. The refined bond lengths included Ga-H 159.0(1l), Ga-P 244.3(6) and P-C 184.0(2) pm, and the HGaP and GaPC angles were 98.4(120 and 117.7(3)"respectively. Calculations at levels up to MP2/6-31 l+G(df,p) gave parameters to within 1 pm or 1" of the experimental values, although some parameters were restrained, so for these comparisons of theory and experiment are not meaningful. In the crystalline phase monomeric adducts were present, with the structure broadly similar to that in the gas phase, but with Ga-P bonds 6 pm shorter and GaPC angles 4" narrower.

4

Compounds of Elements in Group 14

The structure of iodoform in the gas phase was first reported in 1946. The original parameters, reported by Otto Bastiansen working alone, were C-I 212(4) pm and eICI 113.0",while in a new study with no less than five authors the C-I bond length (rg)has been determined to be 214.5(8)pm, with ICI 111.9(7)". The original work, measuring and predicting maxima and minima of the GED scattering intensities manually, was thus remarkably accurate and precise.

5: Gas-phase Molecular Structures Determined by Electron Diffraction

177

The structures of halogenated cyclobutenes have been the cause of some controversy. Hexafluorocyclobutene was shown by GED to have a long unique C-C bond (the one opposite the double bond, at 159.5(16) pm, subsequently revised on reanalysis to 158.2(11) pm. In 1,2-dichloro-3,3,4,4,-tetrafluorocyclobutene the corresponding bond was found to be 159.8(10)pm long. However, microwave studies of these molecules gave shorter distances, 155.2(6) and 155.1(15)pm respectively. A joint analysis of GED data and rotational constants for hexafluorocyclobutene yielded a distance of 158.5(8) pm and, most significantly, fitted the measured rotational constants to within 0.3 MHz. This should end the argument, but it continues. So now perfluoro-bicyclo-[2,2,O]hex- l(4)-ene has been studied." In this molecule there are two cyclobutene rings, sharing the double bond, so the symmetry is D2h, which simplifies the structure determination. In the rg,
178

Spectroscopic Properties of Inorganic and Organometallic Compounds

CCSi and CCCl angles are 128.1(1)and 117.0(2)' respectively, with bond lengths C=C 134.5(3),C-Cl 174.9(1)and C-Si 187.9(2)pm. In Br(SiH3)C=CH2the CCSi and CCBr angles are 125.0(4) and 120.7(4)", and C=C, C-Br and C-Si bond lengths are 133.4(2), 191.0(3)and 187.2(3)pm respectively. Electronegative substituents also affect the ring structure of benzene derivatives, with widening of the ips0 angle and shortening of the adjacent ring bonds. However, there have been relatively few structural studies of benzene derivatives with electron-releasing substituents, which should narrow the ips0 angle, and could even lead to the bond to the substituents lying out of the ring plane. Silyl groups are suitably positive substituents, and structures of phenyl silane and the three disilyl benzenes have now been reported.15The Si-C bond lengths and ips0 CCC angles in the r 2 structures are 186.3(3)pm and 118.2(2)Ofor silyl benzene, 187.5(2) pm and 119.9(2)' for 1,2-disilylbenzene, 187.1(1) pm and 119.4(3)O for 1,3-disilylbenzeneand 186.6(3)and 117.4(2)"for the 1,4-disubstituted compound. The variation in the angles is somewhat surprising, but large effects of the substituents on the ortho CCC angles, and smaller effects on meta angles, account for much of the variation. Both trimethylsilyl and cyclopropyl groups are electron-donating, and can cause lengthening of carbon-carbon triple bonds in adjacent ethynyl groups. In 1,l-bis(trimethylsilylethyny1)cyclopropaneboth groups are able to influence the triple bonds, and so unusually long bonds were expected.16The observed C=C distance [123.9(1) pm, r h l ] was indeed much longer than in propyne [120.5(1) pm]. Interaction of the n orbitals of the triple bond with the ring orbitals is also reflected in the much greater length of the C(ltC(2) bonds [154.5(3) pm] than C(2)-C(3) [148.2(6)pm]. Other refined distances included 42-C 144.6(2),Si-C= 183.5(3)and Si-C(methy1) 187.7(1)pm. Conformational properties of derivatives of butane with silicon replacing carbon in the 1 and 2 positions have been studied by GED and computational methods.17With the silicon atom at the end of the chain, the potential function for rotation about the central C-C bond is similar to that for n-butane, but with the longer Si-C bond at the centre of the 2-substituted compound the energy barriers are much lower. Experimentally 35(5)?40 of 1-silabutane is in the gauche conformation, the remainder being anti, this distribution corresponding to an free energy difference of 1.6(4) kJ mol-'. Computed values lie between 1.4 (MP2/cc-PVTZ) and 3.2 (HF/6-31G*) kJ mol-'. For 2-silabutane 57(9)?40of the molecules were found to be in the gauche conformation, corresponding to the anti conformer having the lower free energy in this case, by 0.7(8) kJ mol-'. Computed values were between 0.3 (HF/6-31G*) and 1.9 kJ mol-', all favouring the anti form. Refined parameters (Y, structure) for the 1-sila compound included Si-C 187.4(2)pm, C-C 153.9 and 153.2(3)pm, SiCC and CCC angles of 113.0(6) and 111.6(6)O respectively, and 73.7(26)' for the SiCCC dihedral angle in the gauche conformer. In the 2-sila compound parameters included Si-C 186.7 and 187.2(2) pm, C-C 154.3(4) pm, CSiC 113.0(8)", SiCC 113.7(5)",and 58.2(34)O for the CSiCC dihedral angle. As part of a systematic study of silacyclobutanes 1,l-diethynylsilacyclobutane has been studied." In the ra structure the bonds from silicon to the ethynyl

5: Gas-phase Molecular Structures Determined by Electron Difraction

179

carbons are short, at 181.7(1)pm. The shortening is attributed to interactions between the outer JI charges of the triple bonds and silicon 3pn orbitals, and is said to be reproduced by ab initio calculations, although the shortest calculated distance is actually 182.9 pm [MP2/6-311+ +G(d,p)]. Other refined distances include Si-C(ring) 187.4(2),C-C 156.3(2) and C=C 120.9(1) pm, and angles of 79.2(6)O between the two ring Si-C bonds, and 106.5(6)' between the two Si-C bonds to the ethynyl groups. These groups are bent 3.1(15)" away from one another at the inner carbon atoms, and the ring puckering angle is 30.0(15)'. The determination of the equilibrium structure of 1,4-disilacyclohexa2,5,diene is particularly interesting, because effects of both a large-amplitude vibration and of anharmonicity were con~idered.'~ The molecule has DZhsymmetry, and there is a low-frequency ring puckering mode (B1, symmetry), which complicates the structural analysis. This mode was treated separately from all others, and the atomic motions were modelled by using a set of pseudo-conformers distributed along the computed pathway. [Calculations were performed at levels up to MP2/6-311++G(df,pd)]. Refinements were based on the GED scattering intensities and five vibrational frequencies, and both geometrical parameters and some force-field scaling factors were refined. Bond lengths included Si-C 186.1(2) and C=C 134.6(3) pm, and the CSiC angle refined to 109.9(3)".The planarity of the ring was unequivocally demonstrated, and highlevel calculations on 1,4-cyclohexa-2,5,diene confirmed that this also is planar, and that there is no need to invoke TC bonding between silicon and the double bonds to explain the planarity. Almost all substituted cyclohexanes have an energetic preference for the equatorial conformer. A report that 1-methyl-1-silacyclohexane shows a preference for the axial conformation, according to room-temperature NMR experiments and molecular mechanics calculations, was therefore surprising. This compound has now been studied by GED, computational methods up to MP2/6-31G* and mPWlPW91/6-311G(2df,p), and NMR spectroscopy in an extreme low-temperature solvent, at 110 KZ0All these methods indicate a modest preference for the axial conformation, with 68(7)0/, of the molecules in this form at room temperature according to the GED data, 68-73% according to the computational methods, and 74(1)0/, at 110 K, according to the NMR spectra. The GED result corresponds to a Gibbs free energy difference of 1.9(6) kJ mol-', and the NMR data give 1.3(1) kJ mol-'. Refined geometrical parameters (structure type not stated) included 186.5(2) pm for the mean Si-C distance, 153.1(2)pm for the mean C-C distance (small differences were fixed at calculated values), 102.8(20)' for the ring CSiC angle, 116.7(34)' for the CCC angle at the opposite end of the ring, 112.4(27)"for the other CCC angles, and 110.5(16)"for the CCSi angles. The position of the methyl group was defined by C(ring)SiC(methyl)angles of 112.5(24)'.

5

Compounds of Elements in Group 15

Molecules of 0-nitrobis(trifluoromethyl)hydroxylamine,(CF3)*NON02, may be

180

Spectroscopic Properties of Inorganic and Organometallic Compounds

regarded as being derived from two stable free radicals, (CF3)2N0and NO2,and it is therefore not surprising that the N-0 bond linking them is unusually long.21 The experimental distance (r,) is 159.7(16) pm, whereas single bond lengths in nitrites are typically around 140 pm. Distances between two electronegative atoms are notoriously difficult to calculate accurately, and with the 6-31G* basis set H F calculations give an N-0 distance that is 20 pm too short, while the MP2 method yields a distance that is too long by 7 pm. The hybrid DFT method, B3LYP, gets to just over 1 pm from the experimental distance, but other functionals, that might be expected to be equally reliable, do not perform so well. Moreover, even in this molecule, B3LYP overestimates the C-N distance by 4 pm. Great care should be taken with any computational method with this sort of compound. The molecule has C, symmetry, with pyramidal coordination at the amino nitrogen atom, a planar NON02 fragment, and the NO2 group anti to the CNC bisector. Other bond lengths are C-F(mean) 132.7(1), C-N 140.8(8), N(amino)-0 139.2(18) and N=O(mean) 119.2(4) pm, while angles include CNC 118.9(8), CNO 110.6(19), NON 106.9(25) and O=N=O 138.4(24)". There is a large tilt of the NO;! group away from the amino nitrogen atom, with the two 0-N=O angles 114.2(21) and 107.5(21)".The lengths of N-0 single bonds in covalent nitrates and nitrites have been reviewed.22Surprisingly, the distance in (CF3)2NON02 is not the same as in the paper devoted to that molecule, being given as 158.8(14)pm. Azoxy compounds have been observed to possess antibacterial, antifungal and antitumour properties, but they are not a general panacea, as azoxymethane has been reported to be carcinogenic. Fluoro(trifluoromethyl)-diazene-2-oxide, CF3N(0)NF, has been prepared by reaction of CF3NO and N2F4, and its structure has been determinedF3The unique fluorine atom is trans to the CF3 group, consistent with both MP2 and B3LYP calculations with the 6-31G* basis set, which place the cis conformer 25 and 21 kJ mol-' respectively higher in energy. However, the calculations also indicate that the isomer CF3NN(0)Fis more stable, by about 50 kJ mol-'. The refined bond lengths (r,) are N=N 128.7(15), N=O 123.1(6), N-F 138.0(6), N-C 149.8(6) and C-F 131.2(3) pm. Angles are NNO 131.2(13),NNF 103.5(13),NNC 114.0(12)and FCF 110.4(6)". There are quite a lot of halonitrobenzenes, and structures of many of them have been determined, but the fluoronitrobenzenes have been missed out. Not any more: the ortho compound has now been studied.24The nitro group is twisted 37.6(30)O out of the ring plane (rg,
5: Gas-phase Molecular Structures Determined by Electron Difraction

181

from the conformations of the methyl groups, the structures of the two molecules are very similar. In the following list of rg and
182

Spectroscopic Properties of Inorganic and Organometallic Compounds

0-C distances 144.1 - 145.1(10) pm. Local asymmetry has also been explored in a study of bis(trichlorosily1)tertbutylphosphine, P B u ' ( S ~ C ~ ~The ) ~ .three ~ ' groups on the phosphorus atom are all twisted 15-20"in the same sense away from the fully staggered positions, at which the molecule would have had C, symmetry. Distortions of the P-CC3 and P-SiC13 fragments away from local C3" symmetry were also included, with flexible restraints based on calculations at the MP2(fc)/6-311G* level. Important refined structural parameters (ra) were P-C 190.6(6), P-&(mean) 221.0(5), CC(mean) 156.5(6)and Si-Cl(mean) 203.2(1) pm, and angles PCC(mean) 109.7(6), CPSi 105.0(7)and 104.5(7),SiPSi 99.9(6)and PSiCl(mean) 111.2". The variations from local symmetry were analysed in terms of axial and equatorial components of tilts of the butyl and trichlorosilyl groups. The tert-butyl group was found to be tilted 6.6" towards the phosphorus lone pair of electrons, with almost no equatorial component. Both trichlorosilyl group have substantial components of tilt towards the phosphorus lone pair, 4.0 and 4.7", but one has an equatorial tilt component of 4.3" towards the butyl group, while the other has an equatorial component of 3.0" away from the butyl group. Similar, but slightly smaller, tilt angles were computed for analogues with one or two SiH3groups, indicating that the steric forces arise primarily from the silicon atoms and the butyl group, and not from the chlorine atoms. C6H4(NMe)2PCl,the fiveIn 2,3-dihydro-1H-1,3,2-benzodiazaphosphole, membered ring includes the NMe-PCl-NMe fragment. Strain in small rings fused to benzene rings were said by Mills and Nixon in 1930 to lead to partial double bond localisation in the adjacent benzene ring, and this molecule has now been studied, to assess both this and anomeric effects.30The observed and computed (RHF/6-3 1lG**) structures are consistent with anomeric effects, with the five-membered ring adopting a non-planar, P-envelope conformation, and with lengthening of the P-Cl bond. Mills-Nixon effects would be shown primarily by changes of angles in the benzene ring, but these are minimal. Calculations on the cation formed by loss of chloride ion show that in this case the whole ion is planar, and the results of the calculations are consistent with a structure that has been determined experimentally. Parameters ( r h l ) for the chloride include P-Cl 218.3(5)and P-N 169.8(4)pm and angles NPCl 103.0(4),NPN 89.1(3)and PNC 112.3(2)".The angle between the NPN and NCCN planes is 21.3(10)'. A study of tetramethylphosphonium fluoride in solid, gas and solution phases31has shown that it exists as PMe4+F- in the crystal and also as a hydrate PMe4+ F(H20)4-,but as trigonal bipyramidal PMe4F in the gas phase. In the gaseous molecules the fluorine atom occupies one axial position, with P-F 175.3(6) pm (structure type not stated), while the axial and equatorial P-C distances are 188.4(8) and 182.6(4)pm respectively. The FPC(equatoria1) angle refined to 84.6(6)", and there is much larger distortion from regular trigonal bipyramidal coordination than has been observed for other methylfluorophosphoranes. HF/6-3 1+G* calculations have reproduced geometries for other methylfluorophosphoranes well, but in this case the P-F distance was too long by 4 pm. The B3LYP/6-31G* method was chosen for deriving vibrational amplitudes, because it was more satisfactory. However, the axial P-C distance

5: Gas-phase Molecular Structures Determined by Electron Difraction

183

given by this method is nearly 3 pm too long, so there is not much improvement. On the other hand, MP2/cc-PVTZ calculations do reproduce the experimental distances very well. Results of a study of the structure of the hydrogen-bonded dimer of dimethylphosphinic acid, [Me2P(=O)OHI2, have been published The two component molecules are linked by a pair of hydrogen bonds between P=O oxygen and hydroxy hydrogen atoms in such a way that the whole P(OH0)2P ring is planar. The length of the hydrogen bond (rhl) refined to 184(2)pm, with the 0 . . . 0 distance 28 l(2)pm, substantially longer than the 248 pm reported for the helical polymer in the crystalline phase. There is an angle of 164(3)O at the hydrogen atom. Experimental distances include P=O 149.7(3), P-0 157.3(4), and P-C 180.6 and 181.1(4)pm, and angles include CP=O 108.8 and 108.6(21), CP-0 193.2(17) and 97.4(20), CPC 119.7(10) and 0-P=O 119.5(5)". Some of these angles differ from those calculated by RHF/6-311G** and B3LYP/631+G** methods by up to 12", which suggests that more of the parameters should have been constrained or restrained.

6

Compounds of Elements in Group 16

Structures of many fluorinated compounds based on central cores of oxygen, sulfur, nitrogen and carbonyl groups have been determined, and the tide is still flowing strongly. Perfluoromethyl fluorocarbonyl peroxide, C F 3 0 0 C ( 0 ) F ,has been shown by IR spectroscopy of argon to exist as a mixture of syn and anti conformers (defined in terms of the orientation of the C=O bond relative to the 0-0 bond). There is just 3% of the anti form at room temperature, corresponding to a free energy difference of 8.8(9) kJ mol-'. Computational methods give Gibbs free energy differences of 3.9 (B3LYP/6-311G*) and 8.5 kJ mo1-l (MP2/6-311G*), and so the GED data were interpreted in terms of a single conformer, with the syn form fitting the data better than the anti. In the refined (r,) structure the COOC dihedral angle refined to 111.2(48)", between those observed in F(CO)OOC(O)F(84")and C F 3 0 0 C F 3(123"),but the 0-0 distances in these three compounds are very similar, in the present case 142.2(15) pm. Other bond lengths are 0-C(carbony1) 137.6(11)and 0-CF3 139.3 (fixed difference), C=O 118.6(8) and C-F(mean) 131.9(4) pm. Angles include OOC(carbonyl) 108.5(9), OOC(F3) 106.7(fixed difference), 0-C=O 129.6(13) and F C F 110.0(9)". Bis(trifluoromethy1) peroxydicarbonate, CF30C(0)OOC(O)CF3,can in principle have many different conformers, but it was believed that the arrangements around 0-C(carbony1) bonds were likely to be syn rather than anti.35B3LYP/63 lG* calculations showed that the syn-syn-syn-syn conformation was lower in energy than anti-syn-syn-syn and syn-anti-syn-syn by 11.7 and 6.1 kJ mol-' respectively, so refinements were based on the lowest-energy form, which had C2 symmetry. The dihedral angle around the central 0-0 bond is 87.1(27)" (ra), typical for a peroxide. Bond lengths include C=O 117.7(4),0-0 140.3(19),and 137.0(5)pm for the average of all the C-0 single bonds, with differences fixed as

184

Spectroscopic Properties of Inorganic and Organometallic Compounds

calculated. The most significant angles are OOC 110.2(13),04-0 102.2(5)and COC 117.3(14)". Methoxycarbonylsulfenyl chloride, CH30C(O)SCl, has the 0-CH3 bond syn with respect to the C=O bond, and a mixture of 72(8)?40syn and 28% anti for the conformation of the S-Cl bond relative to the C=O bond.36In the structural refinements differences between equivalent parameters in the two conformers were fixed, as calculated at the B3LYP/6-311++G** level. Some of these differences are substantial, such as 9.8" for the O=C-S angles and 5.6" for the CSCl angles. Bond lengths (ra) for the syn conformer included C=O 118.5(3)pm, 0-C 132.9(7)and 143.2(fixeddifference)pm for the carbonyl and methyl carbons respectively, C-S 177.8(4) and S-Cl 199.9(2) pm. Angles included O=C-0 129.1(7),O=C-S 126.1(7),COC 114.3(1)and CSCl99.1(3)". Almost all molecules of the type RN=SF2 whose structures have been determined in the gas phase so far have had the syn configuration about the S=N bond, i.e. the sulfur and nitrogen lone pairs of electrons have been eclipsed. The sole exception was FC(0)N=SF(CF3),for which the anti conformer was dominant. This pattern is continued by N-trifluoroacetyl-imidosulfurous difluoride, CF3C(0)N=SF2,37 and [(trifluoroacetyl)imido]-(trifluoromethyl)sulfur fluoride, CF3C(0)N=SF(CF3).38 In the first of these molecules, the C=O bond is also syn to the N-S bond, and conformers other than syn-syn were calculated to be at least 10 kJ mol-' higher in energy (MP2, B3LYP and H F methods with the 6-311G" basis set). Refined parameters (ra) were N=S 148.1(7),N-C 140.6(16), C-C 151.7(10, C=O 120.1(6), C-F 132.7(4) and S-F 158.5(2) pm, with angles SNC 128.2(16),NCO 128.4(17),NCC 109.6(22),FCF 108.7(4),NSF 110.4(12)and FSF 89.3(11)'. It is noteworthy that the B3LYP calculations overestimate the S-F distance by 7 pm, while the MP2 method gives a result that is 5 pm too long. The anomalous conformational behaviour observed for FC(0)N=SF(CF3)is repeated with CF3C(0)N=SF(CF3),38 with the major conformer having the anti arrangement about the N=S bond. Both conformers have the C=O bond syn with respect to N=S. The anti, syn conformer accounts for 90(6)?40 of the gas-phase molecules, corresponding to a Gibbs free energy difference of 5.5( 17) kJ mol-', while B3LYP and MP2 calculations with the 6-31G* basis set give 5.6 and 4.3 kJ mol-' respectively. There is no satisfactory explanation for this behaviour. Replacement of a second fluorine of the SF2 group by another CF3 group might be expected to enhance the stability of the anti conformation, but calculations indicate that in both F(CO)N=S(CF3)2and CF3(CO)N=S(CF3)2 the syn conformation is the more stable, albeit only by 4.2 and 1.7 kJ mol-' respectively. The most significant parameters (ra) for CF3C(O)N=SF(CF3)are N=S 155.4(8),S-F 160.4(6)and S-C 185.3(7)pm, CNS 111.2(11),NCO 129.6(13), NSC 98.2(19) and FSC 94.8(20)",and 163.5(44)"for the CNSC dihedral angle. The expected syn arrangement about the N-S bond is also found in N fluoroformyl-sulfurous dichloride, FC(0)N=SC12,of which 94(8)% of the molecules also have the C=O bond syn to the S=N bond, with the remaining molecules adopting the syn, anti c o n f ~ r m a t i o nThe . ~ ~ gas-phase infrared spectrum has also been interpreted in terms of 5(1)% of the minor form, which give (206)"G' 7.3(6) kJ mol-' for the energy difference, compared with computed

5: Gas-phase Molecular Structures Determined by Electron Dijti-action

185

values of 5.4 (B3LYP/6-31G*)and 6.5 kJ mol-' (MP2/6-31l(2df). Conformers with the anti arrangement about the S=N bond were calculated to be at least 30 kJ mol-' higher in energy. Refined parameters (structure type not given, probably ra) were N=S 151.9(5), S=Cl 206.4(3), C-N 137.2(20), C=O 120.3(6) and C-F 134.8(16) pm, CNS 122.8(17), NCO 129.4(17), NCF 105.9(10), NSCl 110.9(10) and ClSCl98.0(7)".Some computed parameters are far away from the experimental values, particularly the B3LYP S-Cl distance, which is 9 pm too long, while the same method overestimates the CNS angle by 4". Trifluoromethyl chlorosulfonate, CF3OSO2C1,exists in gaseous, liquid and crystalline phases as a single conformer, in which the CF3group is gauche with respect to the S-C1 bond.40The COSCl dihedral angle is 94(3)";this, coupled with the fact that the two S=O bonds are widely spaced [
186

7

Spectroscopic Properties of Inorganic and Organometallic Compounds

Compounds of Transition Elements, Lanthanides and Actinides

Studies of metal halides at elevated temperatures continue to attract attention. Cuprous chloride has been investigated at 689 K, at which temperature Cu3C13 and CuqC14 were identified, and at 1333 K, where the trimers and tetramers were joined by dimers!2 At the lower temperature, the composition (defined in terms of the percentage of the vapour content, which we interpret to be the percentage of the total CuCl present in the various oligomers) was 79.2(9)0/, trimer, while at the higher temperature there was 39.5(14)0/,dimer, 52.2(14)0/,trimer, the remainder being tetramer. MP2/LanL2DZ calculations indicated that all the species were planar, with Cu, rings bridged by chlorine atoms. Structures for these most stable forms were then optimised by MP2, B3LYP and BPW91 methods with the aug-cc-PVTZ basis set for chlorine and a Stuttgart pseudopotential and valence basis set combination for copper. These methods gave substantial differences between some bond lengths, up to 12 pm. Final refined parameters (r,, cu)at 1333 K were Cu-Cu 250.9(13) pm in the dimer, 264.4(12)in the trimer, and 299.9(13) pm in the tetramer, and Cu-Cl 225.4(11), 218.0 and 215.5 pm for the dimer, trimer and tetramer, respectively, with the differences fixed as calculated by the B3LYP method. For the trimer and tetramer at 689 K the Cu-Cu distances were 262.7(12)and 299.7(11)pm, and Cu-Cl bond lengths were 216.6(8) and 214.1 pm. Neodymium diiodide, studied at 795 K, has C2"symmetry, with r,(Nd-I) 297.3(3) pm, 10 pm longer than in NdI3, and
5: Gus-phase Molecular Structures Determined by Electron DiJffraction

187

sets for niobium and 6-311G* for the other atoms, overestimated the bond lengths by 1 to 4 pm, while angles were out by about 1.5" for NbSBr3, but quite accurate for the others. Comparison with structures of other members of the NbYX3 series shows that bond lengths and angles are affected remarkably little by changes of other substituents, a feature that had been noted previously for the tungsten chalcogenide halides, WYXe Metal P-diketonates are of interest as volatile metal-containing compounds. There are many suitable metals and several different ligands, so the scope for structural studies is considerable. Scandium tris-acetylacetonate, SC(CH~COCHCOCH~)~, has a twisted antiprism structure for the Sc06 core, with the triangular O3 faces twisted 26.8(11)' from their positions in a regular prismatic The chelate rings were allowed to deviate from planarity, which would reduce the molecular symmetry from 0 3 to C3, but the fold angle, along the 0 .. . 0 axis of each ligand, refined to 3.0(27)",not significantly different from zero. Other parameters in the ra structure were Sc-0 207.6(4),0-C 127.1(3) and C-C(ring) 138.6(4)pm, with the angle OScO for one ligand 82.4(13), ScOC 132.2(15)and CCC in the ring 123.8(15)". Three other metal P-diketonates have also been studied, all with the dipivaloyl-methanato ligand, in which the methyl groups of acetylacetonato have been replace by t-butyl groups. The structures of the complexes with three of these ligands, abbreviated as dpm or thd, on scandium:* l a n t h a n ~ m ; and ~ erbium" have been determined. All three have D3 symmetry, with planar chelate rings, and twisted antiprism structures for the M 0 6 cores. The twist angles from regular prismatic structures are 25.7( 15)" (scandium), 22.7(21)" (lanthanum) and 20.7(8)"(erbium). In Sc(dpmh the Sc-0,O-C and ring C-C distances (Y,) refined to 206.6(5), 127.2(3) and 138.5(3) pm respectively, and ring angles are OScO 82.4(4), ScOC 132.3(13) and CCC 123.2(15)". Some corresponding parameters determined for L a ( d ~ mare ) ~ La-0 237.1(6), 0-C 127.8(5) and C-C 139.6(7)pm, OLaO 71.4(2) and CCC 123.7(13)".The LaOC angle is not listed. In the erbium compound parameters include Er-0 221.8(5),0-C 127.9(5)and C-C 140.4(6)pm and OErO 75.0(4)". A P-diketonate ligand also features in Cu(1,5-cod)(hfac) [also known as tanedionato)(y2-1,5-cyclooctadiene)copper(I)], (1,1,1,5,5,5-hexafluor0-2,4-pen where its important role is to make the compound volatile. Decomposition on a heated substrate by the disproportionation reaction Cu'(P-diketonate)L

-+

Cuo + Cur'(P-diketonate)2 + 2L

leads to the deposition of copper as a conducting layer, with all other products being volatile. The structure of this compound has been determined?l and it has been shown to exist in a form in which one olefinic group of the cyclooctadiene ligand is coordinated to the square-planar copper atom. The ring has a twistboat conformation, which allows the second ring double bond to be weakly associated with the metal atom, with Cu . . . C distances of 267.2(23) and 276.9(25) pm, and gives the molecule overall C1 symmetry. Calculations (BP86/AE1) showed that a transition state for switching of the coordination of the two double bonds was just 2.3 kJ mol-' higher in energy than the ground state, while two

188

Spectroscopic Properties of Inorganic and Organometallic Compounds

structures with the ligand in chair conformations were 10 and 14 kJ mol-' above the minimum. In the ra structure, Cu-C bonded distances were 194.0 and 194.9(13) pm, and the Cu-0 distance was 194.4(9) pm, with the hfac ligand assumed to have local C2usymmetry. The length of the coordinated C=C bond was refined to 142.9(7) pm, with the length of the weakly coordinated bond 135.3(19) pm. These parameters, and an analysis of bond critical paths, are consistent with the Dewar-Chatt-Duncanson bonding model, based on 0 donation from the olefin to the metal and n back-donation from the metal to the olefin. However, bonding to the more distant olefin involves little disturbance of the charge distribution by the metal, although the energy of this 'weak' interaction is calculated to be 26 kJ mol-'. Few complexes containing C5F5 ligands are known, and Ru(C5Me5)(C5F5) is the first to have its gas-phase structure determined.52 Calculations (B3PW91/LanL2DZ) were also performed this compound, and for complexes with all combinations of C5F5 and CsH5 ligands. The effect of the fluorine substituents is to reduce the distance between the ring and the metal atom [to 177.9(2)pm (ra)in Ru(C5Me5)(C5F5) compared with 183.7pm in Ru(C~H~)~], but it also lengthens the distance to the other ring by a few pm. So replacing both C5HS rings in ruthenocene by C5F5leads to a shortening of only 0.7 pm. Curiously, the distance to the C5Me5ring is also slightly reduced [calculated 182.2 pm, experimental 183.6(2) pm]. Ring substituents were also found to tilt away from the ruthenium atom in all cases, by 4.2(6)"for the C-F bonds and 2.1(11)O for the C-C(Me) bonds, so this property is also not a simple function of substituent electronegativity. The two rings are very nearly perfectly eclipsed, the small deviation arising from the conformation of the methyl groups, each of which has one C-H bond more or less in its local ring plane. The possibility that ethyltrioxorhenium(VII), C2HSReO3, might show an agostic interaction has been investigated, but the structure turns out to be classical.53 DFT calculations were carried out using two methods, first BPW91 with a Hay and Wadt quasi-relativistic ECP basis set on rhenium and Dunning basis sets for the other atoms, and secondly using a triple-c basis set of Slater-type orbitals, with relativistic corrections. These calculations showed that the CRe03 core could be regarded as having C3ulocal symmetry, which was assumed in the GED analysis. Overall the molecule has C, symmetry, with a staggered conformation. Refined parameters (r,) included Re-C 209.5(6) and Re-0 171.1(2) pm, with angles OReC 104.6(5)and ReCC 112.0(9)". In both zirconium tetrakis(tetrahydroborate), ZT(BH~)~, and its uranium analogue, U(BH4)4,the tetrahydroborate groups are triply bridged to the metal atoms, which therefore have a formal coordination number of In the zirconium compound, DFT calculations with Slater-type orbitals show that the four ligands are twisted about 12"away from the perfectly staggered positions, reducing the symmetry from Td to T, while the GED data lead to a value of 15(2)" for this parameter. The Zr-B distance (ra) refined to 232.4(5) pm, with Zr-H 214.4(6)pm, and the bridging and terminal B-H distances 127.8(8)and 118.8(17) pm respectively. In the uranium compound the calculations show that the twisting of the ligands does not occur, so that Td symmetry is maintained. The

5: Gas-phase Molecular Structures Determined by Electron Diflaction

189

U-B and U-H bond distances are 251.2(4) and 231.5(6) pm, with bridging and terminal B-H distances 131.6(5) and 117.8(11) pm.

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