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Nuclear Magnetic Resonance Volume 36 A Specialist Periodical Report Nuclear Magnetic Resonance Volume 36 A Review of ...

Author: Graham A Webb

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Nuclear Magnetic Resonance Volume 36

A Specialist Periodical Report

Nuclear Magnetic Resonance Volume 36 A Review of the Literature Published between June 2005 and May 2006 Editor G.A. Webb, formerly Department of Chemistry, University of Surrey, Guildford, UK Authors A.E. Aliev, University College London, UK N. Asakawa, Tokyo Institute of Technology, Tokyo, Japan A.C. de Dios, Georgetown University, Washington, DC, USA H. Fukui, Kitami Institute of Technology, Kitami, Japan E.F. Hounsell, Birkbeck University of London, UK C.J. Jameson, University of Illinois at Chicago, USA K. Kamien´ska-Trela, Polish Academy of Sciences, Warszawa, Poland S. Kuroki, Tokyo Institute of Technology, Tokyo, Japan H. Kurosu, Nara Women’s University, Nara City, Japan R.V. Law, Imperial College of Science and Technology, London, UK R. Ludwig, University of Rostock, Germany S.J. Matthews, Imperial College London, UK M. Monduzzi, University of Cagliari, Italy S. Murgia, University of Cagliari, Italy D. Nietlispach, University of Cambridge, UK M.J.W. Prior, University of Nottingham, UK W. Schilf, Polish Academy of Sciences, Warszawa, Poland T. Watanabe, Aoyama Gakuin University Women’s College, Tokyo, Japan J. Wo´jcik, Polish Academy of Sciences, Warszawa, Poland T. Yamanobe, Nara Women’s University, Nara City, Japan H. Yasunaga, Kyoto Institute of Technology, Kyoto, Japan

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ISBN-10: 0-85404-362-4 ISBN-13: 978-0-85404-362-0 ISSN 0305-9804 A catalogue record for this book is available from the British Library r The Royal Society of Chemistry 2007 All rights reserved Apart from any fair dealing for the purpose of research or private study for non-commercial purposes, or criticism or review as permitted under the terms of the UK Copyright, Designs and Patents Act, 1988 and the Copyright and Related Rights Regulations 2003, 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 UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. 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 0WF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Typeset by Macmillan India Ltd, Bangalore, India Printed and bound by MPG Books Ltd, Bodmin, Cornwall, UK

Preface G. A. Webb DOI: 10.1039/b615948f It is a pleasure for me to introduce Volume 36 of the Specialist Periodical Reports on NMR which comprises the familiar comprehensive annual coverage of the appropriate literature. In this case that appearing between June 2005 and May 2006. Three changes to the reporting team are noted with this volume. M. Monduzzi and S. Murgia, who have been covering Liquid Crystals and Micellar Solutions, and S. J. Matthews who has reported on NMR of Proteins and Nucleic Acids, are retiring. At the same time D. Nietlispach is joining the team with his account of Multiple Resonance. It is my pleasure to thank them, and all the other reporters for their timely and interesting accounts.

Royal Society of Chemistry, Burlington House, Piccadilly, London, UK W1J 0BA. E-mail: [email protected]

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CONTENTS Cover 3D illustrated atom. Image courtesy of Bruker BioSpin Ltd.

Preface

7

G. A. Webb

NMR books and reviews

22

W. Schilf Books Regular reviews series Edited books and symposia Reviews in periodicals Reviews and books in foreign languages

22 22 22 22 22

Theoretical and physical aspects of nuclear shielding

50

Cynthia J. Jameson and Angel C. de Dios Theoretical aspects of nuclear shielding Physical aspects of nuclear shielding

50 58

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Applications of nuclear shielding

72

Shigeki Kuroki, Naoki Asakawa and Hidekazu Yasunaga Introduction Shielding of particular nuclear species

72 72

Theoretical aspects of spin–spin couplings Hiroyuki Fukui Introduction NMR spectroscopy and chirality Relativistic calculation of spin–spin coupling constants Relationships between spin–spin coupling constants and structures Assessment of density functional theory Hydrogen bonding eﬀects on nuclear spin–spin coupling constants Conformational analysis

113 113 113 114 116 121 122 123

Applications of spin–spin couplings

131

Krystyna Kamien´ska-Trela and Jacek Wo´jcik Introduction New methods One-bond couplings to hydrogen One-bond couplings not involving hydrogen Two-bond couplings to hydrogen Two-bond couplings not involving hydrogen Three-bond hydrogen–hydrogen couplings Three-bond couplings to hydrogen Three-bond couplings not involving hydrogen Couplings over more than three bonds and through space Couplings through hydrogen bonds Residual dipolar couplings

131 132 134 135 141 142 143 147 151 152 154 154

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Nuclear spin relaxation in liquids and gases R. Ludwig Introduction General, physical and experimental aspects of nuclear spin relaxation Selected applications of nuclear spin relaxation Nuclear spin relaxation in gases Self-diﬀusion in liquids

170 170 171 183 186 188

Solid-state NMR spectroscopy A. E. Aliev and R. V. Law Introduction Reviews Experimental developments Distance and angle measurements by solid-state NMR NMR parameters: experimental and theoretical studies Applications

196

Multiple pulse NMR

244

Daniel Nietlispach Introduction General methods and theoretical developments Fast multidimensional methods Spin relaxation methods Diﬀusion experiments Coupling constant measurement Residual dipolar couplings Homonuclear spectroscopy Inverse proton detected correlation spectroscopy

244 244 245 249 252 253 254 255 256

NMR of proteins and nucleic acids S. J. Matthews Introduction New methodology Macromolecular structures Protein folding

196 196 200 207 209 212

262 262 262 270 278

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NMR of carbohydrates, lipids and membranes

285

Elizabeth Hounsell Introduction Glycosylated protein conformation and folding Studies of proteins and small molecules in membranes Oligosaccharide conformation, recognition and function Metabolomic studies and hyphenated techniques Bacterial polysaccharides Phytotherapeutics Other natural products Materials science

285 285 287 291 293 295 297 299 300

Synthetic macromolecules Hiromichi Kurosu and Takeshi Yamanobe Introduction Primary structure Liquid crystalline polymers Imaging and diﬀusion Characterization of the synthetic macromolecules Polymer blend of the synthetic macromolecules Dynamics of the synthetic macromolecules

309

NMR in living systems

344

Malcolm J. W. Prior General applications and methodologies Cells Plants Tissues Clinical

344 348 350 351 355

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309 309 309 318 319 326 328

Nuclear magnetic resonance imaging

363

By Tokuko Watanabe Introduction Introductory articles and reviews Instruments Pulse sequences and data processing Other nuclei Dynamics: diﬀusion, ﬂow, and velocity Polymer Plant, seed, fruit Food In vivo application

363 363 365 370 373 376 382 384 385 387

NMR of liquid crystals and micellar solutions

397

Maura Monduzzi and Sergio Murgia Introduction General articles: reviews, methods, models Liquid crystals Micellar solutions

397 398 399 408

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Symbols and Abbreviations These lists contain the symbols and abbreviations most frequently used in this volume, but they are not expected to be exhaustive. Some specialized notation is only deﬁned in the relevant chapter. An attempt has been made to standardize usage throughout the volume as far as is feasible, but it must be borne in mind that the original research literature certainly is not standardized in this way, and some diﬃculties may arise from this fact. Trivial use of subscripts etc. is not always mentioned in the symbols listed below. Some of the other symbols used in the text, e.g. for physical constants such as h or p, or for the thermodynamic quantities such as H or S, are not included in the list since they are considered to follow completely accepted usage.

Symbols aN A

B

B0 B1, B2 Cx CJ, C> D D DJ, D> Dint D0 E En g G Hij H Ii Iix, Iiy, Iiz

hyperline (electron–nucleus) interaction constant (i) hyperﬁne (electron–nucleus) interaction constant (ii) parameter relating to electric ﬁeld eﬀects on nuclear shielding (i) magnetic induction ﬁeld (magnetic ﬂux density) (ii) parameter relating to electric ﬁeld eﬀects on nuclear shielding static magnetic ﬁeld of NMR or ESR spectrometer r.f. magnetic ﬁelds associated with n1, n2 spin-rotation coupling constant of nucleus X 2 (used sometimes in tensor form): C 2 ¼ 1=3ðCJ2 þ 2C> Þ components of C parallel and perpendicular to a molecular symmetry axis (i) self-diﬀusion coeﬃcient (ii) zero-ﬁeld splitting constant rotational diﬀusion tensor components of D parallel and perpendicular to a molecular symmetry axis internal diﬀusion coeﬃcient overall isotropic diﬀusion coeﬃcient electric ﬁeld ^ (or a contribution to H) ^ eigenvalue of H nuclear or electronic g-factor magnetic ﬁeld gradient element of matrix representation of H Hamiltonian operator–subscripts indicate its nature nuclear spin operator for nucleus i components of Ii

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I n

J

Jr J n K mi M0 M x , M y, M z Mn PA Pi Puv q Q sA 2 SA (0) S

t T Tc Tg TX 1 TX 2 T 02 T2 T3 X TX 1p ,T 2p T1D Xi ZA

(i) ionization potential (ii) moment of inertia nuclear spin–spin coupling constant through n bonds (in Hz). Further information may be given by subscripts or in brackets. Brackets are used for indicating the species of nuclei coupled, e.g. J (13C, 1H) or additionally, the coupling path, e.g. J(POCF) reduced splitting observed in a double resonance experiment rotational quantum number reduced nuclear spin–spin coupling constant (see the notes concerning nJ) eigenvalue of Iiz (magnetic component quantum number) equilibrium macroscopic magnetization of a spin system in the presence of B0 components of macroscopic magnetization the number of average mol. wt. valence p orbital of atom A fractional population (or rotamers etc.) element of bond-order, charge-density matrix electric ﬁeld gradient (i) nuclear quadrupole moment (ii) quality factor for an r.f. coil valence s-orbital of atom A electron density in SA at nuclear A (i) singlet state (ii) electron (or, occasionally, nuclear spin) cf. I (iii) ordering parameter for oriented systems (iv) overlap integral between molecular orbitals elapsed time (i) temperature (ii) triplet state coalescence temperature for an NMR spectrum the glass transition temperature (of a polymer) spin–lattice relaxation time of the X nuclei (further subscripts refer to the relaxation mechanism) spin–spin relaxation time of the X nucleus (further subscripts refer to the relaxation mechanism) inhomogeneity contribution to dephasing time for Mx or My total dephasing time for Mx or My; (T2*)1¼T21 þ (T2 0 )1 decay time following 900t9090 pulse sequences spin–lattice and spin–spin relaxation time of the X nuclei in the frame of reference rotating with B1 dipolar spin–lattice relaxation time mole fraction of compound atomic number of atom A

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a

b gX dX

dij d(rKA) D DJ Dn Dd Dn 12 Ds Dw er e0 Z

m m0 mB mN ni n0 n1 n2 si

sJ,s> sd sp t tc

(i) nuclear spin wavefunction (eigenfunction of Iz) for a spin 12 nucleus (ii) polarizability nuclear spin wavefunction (eigenfunction of Iz) for a spin 12 nucleus magnetogyric ratio of nucleus X chemical shift of a nucleus of element X (positive when the sample resonates to high frequency of the reference). Usually in p.p.m. Kronecker delta (¼1 if i ¼ j, and ¼0 otherwise) Dirac delta operator (i) time between ﬁeld gradient pulses (ii) spectral width anisotropy in J (DJ ¼ JJJ>, for axial symmetry) population diﬀerence between nuclear states change of diﬀerence in d full width (in Hz) of a resonance line at half-height (i) anisotropy in s(Ds ¼ sJs>, for axial symmetry) (ii) diﬀerences in s for two diﬀerent situations (i) susceptibility anisotropy(Dw ¼ wJw>, for axial symmetry) (ii) diﬀerences in electronegativities relative permittivity permittivity of a vacuum (i) nuclear Overhauser eﬀect (ii) asymmetry factor (e.g. in e2 qQ=h) (iii) refractive index (iv) viscosity magnetic dipole moment permeability of a vacuum Bohr magneton nuclear magneton Larmor precession frequency of nucleus i (in Hz) (i) spectrometer operating frequency (ii) Larmor precession frequency (general, or of bare nucleus) frequency of ‘observing’ r.f. magnetic ﬁeld frequency of ‘irradiating’ r.f. magnetic ﬁeld shielding parameter of nucleus i (used sometimes in tensor form). Usually in p.p.m. Subscripts may alternatively indicate contributions to s. components of s parallel and perpendicular to a molecular symmetry axis diagrammatic contribution to s paramagnetic contribution to s (i) pre-exchange lifetime of molecular species (ii) time between r.f. pulses (general symbol) correlation time

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tcoll tj tp tt w o oi, o0, o1, o2 om or

mean time between molecular collisions in the liquid state angular momentum correlation time pulse duration translational magnetic relaxation correlation time (i) magnetic susceptibility (ii) electronegativity (iii) nuclear quadrupole coupling constant (¼ e2 qQ=h) carrier frequency in rad s1 as for n i , n 0 , n 1 , n 2 but in rad s1 modulation angular frequency (in rad s1) sample rotation (rad s1)

Abbreviations (a) Physical properties a.f. audiofrequency a.u. atomic unit a.m. amplitude modulation b.c.c. body-centred cubic c.m.c. critical micelle concentration e.d. electron diﬀraction e.f.g. electric ﬁeld gradient f.c.c. face-centred cubic f.m. frequency modulation h.c.p. hexagonal close-packed h.f. hyperﬁne i.d. inside diameter i.f. intermediate frequency l.c. liquid crystalline mol.wt. molecular weight o.d. outside diameter p.p.m. parts per million r.f. radiofrequency r.m.s. root mean square s.h.f. super-high frequency u.h.f. ultra-high frequency ADC analogue-to-digital converter AEE average excitation energy approximation AQ acquire ARP adiabatic rapid passage BIRD bilinear rotation decoupling CCPPA coupled cluster polarization propagator approximation CH-COSY carbon-hydrogen correlation spectroscopy CHESS chemical shift selection

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CHF CIDEP CIDNP COSY CP CPMG CSA CSI CW DAC DD DEPT DLB DNP DQ DQF ECOSY EHT ENDOR EOM ESR EXSY FC FID FLASH FPT FT GIAO HMQ HOHAHA HRPA IDESS IGLO INADE-QUATE INDO INDO/S INDOR INEPT IR ISIS LIS

coupled Hartree–Fock molecular orbital calculations chemically induced dynamic electron polarization chemically induced dynamic nuclear polarization correlation spectroscopy cross polarization Carr–Purcell pulse sequence. Meiboom–Gill modiﬁcation chemical shielding anisotropy chemical shift imaging continuous wave digital-to-analogue converter dipole-dipole (interaction or relaxation mechanism) distortionless enhancement by polarization transfer diﬀerential line broadening dynamic nuclear polarization double quantum double quantum ﬁlter exclusive correlation spectroscopy extended Hu¨ckel molecular orbital theory electron–nucleus double resonance equations of motion electron spin resonance exchange spectroscopy Fermi contact free induction decay fast low angle shot ﬁnite perturbation theory Fourier transform gauge included atomic orbitals heteronuclear multiquantum homonuclear Hartman–Hahn higher random phased approximation improved depth selective single surface coil spectroscopy individual gauge for diﬀerent localized orbitals incredible natural abundance double quantum transfer experiment intermediate neglect of diﬀerential overlap intermediate neglect of diﬀerential overlap calculations for spectroscopy internuclear double resonance insensitive nuclei enhanced by polarization transfer infrared image selected in vivo spectroscopy lanthanide induced shift

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LORG LSR MASS MBPT MEM MINDO MQ MQC MQF NMR NOE NOESY NQCC NQR PFG PRE QF QPD REX

local origin lanthanide shift reagent magic angle sample spinning many body perturbation theory maximum entropy method modiﬁed INDO multiple quantum multiple quantum coherence multiple quantum ﬁlter nuclear magnetic resonance nuclear Overhauser enhancement nuclear Overhauser enhancement spectroscopy nuclear quadrupole coupling constant nuclear quadrupole resonance pulsed ﬁeld gradient proton relaxation enhancement quadrupole moment/ﬁeld gradient quadrature phase detection relativistically extended Hu¨ckel molecular orbital theory rotating frame Overhauser enhancement spectroscopy random phase approximation self consistent perturbation theory spin dipolar spin echo correlation spectroscopy spin echo Fourier transform slice interleaved depth resolved surface coil spectroscopy second order polarization propagator approach selective population inversion selective population transfer spin rotation (interaction or relaxation mechanism) tip angle reduced T1 imaging total correlation spectroscopy ultraviolet Waugh, Huber and Ha¨berlen (cycle of pulses) zero quantum zero quantum coherence

ROESY RPA SCPT SD SECSY SEFT SLITDRESS SOPPA SPI SPT SR TART TOCSY UV WAHUHA ZQ ZQC (b) Chemical speciesa acac ACTH ADP a

acetylacetonato adrenocorticotropic hormone (corticotropin) adenosine diphosphate

Lower case initials are used when the species is a ligand.

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AMP ATP BSA CMP cp DAP DME DMF DML DMS DMSO DNA DPG DPI dpm DPPH DSS DTBN EBBA EDTA EVA fod HAB HMPA HOAB IHP KDP MBBA NADH(P) NMF PAA PBA PBLG PC PCB PDMS PMA PMMA POM PS PTFE PVC

adenosine monophosphate adenosine triphosphate bovine serum albumin cytidine monophosphate cyclopentadienyl dodecylammonium propionate 1,2-dimethoxyethane dimethylformamide dimyristoyl-lecithin dimethylsiloxane dimethyl sulfoxide deoxyribonucleic acid 2,3-diphosphoglycerate dipalmitoyl-lecithin dipivaloylmethanato diphenylpicrylhydrazyl 2,2-dimethyl-2-silapentane-5-sulfonate (usually as the sodium salt) di-t-butyl nitroxide N-(p-ethoxybenzylidene)-p-butylaniline ethylenediaminetetra-acetic acid ethylene-vinyl acetate 1,1,1,2,2,3,3-heptaﬂuoro-7,7-dimethyloctane-4, 6-dionato 4,4 0 -bis(heptyl)azoxybenzene hexamethylphosphoramide p-n-heptyloxyazoxybenzene inositolhexaphosphate potassium dihydrogen phosphate N-(p-methoxybenzylidene)-p-butylaniline nicotinamide adenine dinucleotide (phosphate) N-methylformamide p-azoxyanisole pyrene butyric acid poly(L-benzyl m-glutamate) phosphatidyl choline (lecithin) polychlorinated biphenyl polydimethylsiloxane poly(methacrylic acid) poly(methyl methacrylate) poly(oxymethylene) phosphatidylserine polytetraﬂuoroethylene poly(vinyl chloride)

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PVF PVP RNA SDS TAB TCNQ TFA THF TMS UTP

poly(vinyl ﬂuoride) poly(vinyl pyrrolidone) ribonucleic acid (tRNA, transfer RNA) sodium dodecyl sulfate trimethylammonium bromide tetracyanoquinodimethane triﬂuoroacetic acid tetrahydrofuran tetramethylsilane uridine triphosphate

Amino-acid residues Ala alanine Arg arginine Asn asparagine Asp aspartic acid Cys cysteine Gln glutamine Glu glutamic acid Gly glycine His histidine Hyp hydroxyproline Ile isoleucine

Leu Lys Met Phe Pro Ser Thr Trp Tyr Val

leucine lysine methionine phenylalanine proline serine threonin tryptophan tyrosine valine

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NMR books and reviews W. Schilf DOI: 10.1039/b618335m

1

Books

See ref. 1–3.

2

Regular reviews series

See ref. 4–118.

3

Edited books and symposia

See ref. 119–264.

4

Reviews in periodicals

See ref. 265–525.

5

Reviews and books in foreign languages

See ref. 526–656. Czech See ref. 526. Chinese See ref. 527–554. Croat See ref. 555. Danish See ref. 556–557. French See ref. 558–562. German See ref. 563–566. Greek See ref. 567. Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw 42, POB 58, Poland

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Hungarian See ref. 568–572. Japanese See ref. 573–634. Polish See ref. 635–650. Russian See ref. 651–653. Slovakian See ref. 654. Spanish See ref. 655–656.

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522 Y. Yoshida, S. Matsui and T. Fujita, Bis(pyrrolide-imine) Ti Complexes with MOA: A New Family of High Performance Catalysts for Oleﬁn Polymerization, J. Organomet. Chem., 2005, 690, 4382. 523 X.-H. Zhu, N. Zhang, Y. Zhang, X. Zhang, K. Ugurbil and W. Chen, In vivo 17O NMR Approaches for Brain Study at High Field, NMR Biomed., 2005, 18, 83. 524 S. I. Zones, S.-J. Hwang, S. Elomari, I. Ogino, M. E. Davis and A. W. Burton, The Fluoride-Based Route to All-Silica Molecular Sieves: A Strategy for Synthesis of New Materials Based upon Close-Packing of Guest-Host Products, C. R. Chim., 2005, 8, 267. 525 C. Zwingmann and R. Butterworth, An Update on the Role of Brain Glutamine Synthesis and Its Relation to Cell-Speciﬁc Energy Metabolism in the Hyperammonemic Brain: Further Studies Using NMR Spectroscopy, Neurochem. Int., 2005, 47, 19. 526 J. Brus, Principles and Applications of Multidimensional NMR Spectroscopy of Solid State Natural Isotope Abundance, Chem. Listy, 2005, 99, 99. 527 J. C. C. Chan, Solid-State NMR Study of Microporous and Mesoporous Materials, Huaxue, 2005, 63, 207. 528 J.-f. Chen and Y.-h. Gao, Spectroscopic Investigation of Magnetic Field Eﬀects on Radical Reactions Induced by Laser Excitation, Guangpuxue Yu Guangpu Fenxi, 2005, 25, 1013. 529 M. Chen, Y. Zhang and X. Gan, Structural Analysis of Hydroxypropyl Oligo-Glucomannuronate Sulfate, Wuhan Ligong Daxue Xuebao, 2003, 25, 26. 530 W. Chen, M. Huang, K. Huang, Z. Min and Q. Zhang, TheAdvance of Analytical Techniques for Combinatorial Chemistry, Huaxue Tongbao, 2005, 68, w125/1. 531 Y. Cuo, Application of Liquid Chromatography/Spectroscopy (UV, MASS and NMR) Hyphenated Technology in Study on Bioactive Substances from Traditional Chinese Herbs, Tianran Chanwu Yanjiu Yu Kaifa, 2003, 15, 456. 532 S. Ding, Z.-H. Liu, J.-M. Chen and K.-D. Li, Spin Diﬀusion of Half-Odd-Integer Quadrupolar Systems in Solids, Huaxue, 2005, 63, 193. 533 C. Fan, M. Fan and J. Sheng, Nuclear Magnetic Resonance Study on Water and Its Application in Food Science, Shipin Gongye Keji, 2003, 24, 98. 534 H. Gao, Applications of NMR Technique in Oils and Foods, Zhongguo Youzhi, 2003, 28, 40. 535 C.-M. Hsua, H.-H. Menga, W.-T. Chang, L.-L. Choa and S.-M. Wang, Application of Analytical Methods for Forensic Science, Huaxue, 2005, 63, 1. 536 C. Li, S. Tian, A. Gong and Z. Liu, Applications of Instrumental Analysis Techniques in Petroleum Product Analysis, Fenxi Yiqi, 2004, 4, 1. 537 X.-l. Liao and D.-h. Lin, Protein Dynamics Studied by Heteronuclear Multi-Dimensional NMR, Bopuxue Zazhi, 2004, 21, 385. 538 D.-h. Lin and J. Hong, Mapping Protein-Ligand Interaction by NMR Techniques: A Review, Bopuxue Zazhi, 2005, 22, 321. 539 D.-h. Lin and X.-h. Liu, Residual Dipolar Couplings and Their Applications in Determination of Protein Structures, Bopuxue Zazhi, 2005, 22, 85. 540 K. Lin, Q. You, D. Lin, W. Wu and B. Ye, Biol. NMR in Drug Design, Zhongguo Yaoke Daxue Xuebao, 2004, 35, 387. 541 A.-h. Liu, S.-z. Mao and Y. r. Du, NMR Studies of Gemini Surfactants: Recent Progresses and Prospect, Bopuxue Zazhi, 2005, 22, 223. 542 D. Liu, X. Zhang, N. Wang and X. Yao, NMR Spectroscopy Features of Triterpenoid Saponins from Ardisia, Shenyang Yaoke Daxue Xuebao, 2004, 21, 394. 543 H. Liu, X.-f. Bai and Y.-g. Du, Progresses on Isolation and Structural Analysis of Oligosaccharides, Jingxi Yu Zhuanyong Huaxuepin, 2005, 13, 1. 544 Y.-j. Qiu, S.-a. Xia, C.-h. Ye and M.-l. Liu, Pattern Recognition Methods in Biomedical Magnetic Resonance, Bopuxue Zazhi, 2005, 22, 99. 545 A. Song, S. Dong, J. Hao and H. Wang, NMR Studies of Self-Assembly of Amphiphiles, Huaxue Wuli Xuebao, 2005, 18, 289. 546 J. Sun and Z. Zhang, The Applications of NMR Quantiﬁcation in Analysis of Drugs, Yaowu Fenxi Zazhi, 2005, 25, 117. 547 W. Sun and Z. Shen, Progress in Study on Synthesis and Magnetic Properties of Novel Polymer Complexes Containing Bithiazole Ring, Gaofenzi Xuebao, 2005, 5, 641. 548 C. Xiao, X. Zhang, M. Liu and J. Chang, Solvent Suppression in NMR Spectroscopy, Huaxue Tongbao, 2005, 68, 179. 549 N. Yao, W. He, G. Liu and K. S. Lam, Applications of Nuclear Magnetic Resonance Spectroscopy (NMR) to Combinatorial Chemistry, Huaxue Jinzhan, 2004, 16, 696. 550 X. Wang, Application of Modern Analytic Techniques in Chinese Materia Medica Fingerprinting, Zhongcaoyao, 2004, 35, App.6. 551 S. Wei, C. Zhang, X. Wu, J. Jia and X. Xu, Advances in Characterization of Methylaluminoxane, Shihua Jishu Yu Yingyong, 2005, 23, 477.

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552 A. Zhang, Synthesis, Characterization and Applications of Dendronized Polymers, Huaxue Jinzhan, 2005, 17, 157. 553 Q. Zhao and D.-H. Zeng, Phosphorus Cycling in Terrestrial Ecosystems and Its Controlling Factors, Zhiwu Shengtai Xuebao, 2005, 29, 153. 554 J. Zheng, W. Ran, Z. Zhong and J. He, Research Advance in Polyphosphate-Accumulating Microorganisms in Enhanced Biological Phosphorus Removal Process, Yingyong Shengtai Xuebao, 2004, 15, 1487. 555 V. Simunic-Meznaric and H. Vancik, Nitroso Compounds as Monomers and Dimers, Kem. Ind., 2005, 54, 11. 556 F. H. Larsen and S. B. Engelsen, Wine Analysis by NMR Spectroscopy and Chemometrics, Dan. Kemi, 2005, 96, 27. 557 N. Viereck, H. F. Seefeldt, M. H. M. Hielsen and S. B. Engelsen, HR MAS NMR Spectroscopy: A Whole New World for Food Research, Dan. Kemi, 2005, 86, 30. 558 B. Garrigues and B. Oussaid, Improvement in Determination of the Conformation in Solution of Thiophene Compounds, J. Nat., 2004, 16, 21. 559 S. Laurent, L. Vander Elst and R. N. Muller, Contrast Agents for Molecular Imaging: New Developments and Future, Chim. Nouv., 2005, 23, 22. 560 L. Montagne and L. Delevoye, Recent Developments in Solid State NMR and Their Applications to the Structural Characterization of Vitreous Materials, Spectra Anal., 2005, 34, 26. 561 G. Roth and T. Richert, Very-High-Field Superconducting Magnets for NMR, Spectra Anal., 2005, 34, 43. 562 X. H. Zhang, B. Bureau, J.-L. Adam and J. Lucas, Chalcogenide Glasses: Structure and Optical Functions, Verre (Paris, Fr.), 2004, 10, 22. 563 K. Albert, HPLC-NMR Coupling, Nachr. Chem., 2006, 54, 428. 564 S. Braese, F. Wuerthner, C. Tschierske, A. Krueger, K. Ditrich, R. Pfau, H. Priepke, R. Breinbauer, H.-A. Wagenknecht, G. Draeger, A. Kirschning, N. Sewald, U. Beifuss, M. O. Senge, T. J. J. Mueller, P. R. Schreiner, R. Gschwind, B. F. Straub, K. Muniz, M. Oestreich, J. Pietruszka, T. Lindel, R. Suessmuth, P. Bisel, M. Mueller, E. Weinhold, A. Laeschke, M. Albrecht, T. Bach, G. Bucher, H. Heydt and J. Hartung, Organic Chemistry 2005, Nachr. Chem., 2006, 54, 241. 565 C. Hahn, Substitution Versus Addition—Dicationic Palladium(II)- and Palladium(II)Oleﬁn Complexes and Their Reactions with Protic Nucleophiles, Nova Acta Leopold., Suppl., 2004, 18, 49. 566 G. Schoen and A. Shnirman, Qubits (Almost) to Handle. Solid State Systems, Especially Josephson Contacts, Suitable for Quantum Information Processing, Phys. J., 2005, 4, 51. 567 G. A. Kapoulas, Use of Nuclear Magnetic Resonance Spectroscopy (NMR) to Assess the Authenticity and Quality of Olive Oil: A Brief Review, Pharmakeutike, 2005, 18, 94. 568 G. Batta, Modern NMR Measurement Techniques, Magy. Kem. Foly., Kem. Kozl., 2004, 109–110, 127. 569 I. Klebovich, New Bioanalytical Investigation Trends in Pharmacokinetics and Drug Metabolism Research, Magy. Kem. Foly., Kem. Kozl., 2005, 111, 129. 570 P. Sohar, The NMR Story, Magy. Kem. Foly., Kem. Kozl., 2004, 109–110, 120. 571 G. Szalontai, Anisotropic NMR. Measurement in the Solid and Partially Oriented Phases, Magy. Kem. Foly., Kem. Kozl., 2004, 109–110, 143. 572 K. Tompa, The Origins of NMR Spectroscopy in Hungary, Magy. Kem. Foly., Kem. Kozl., 2004, 109–110, 148. 573 M. Ago, K. Sato and K. Okajima, Structural Change of Cellulose Caused by Hydrophobic Solvent Treatment, Cellul. Commun., 2005, 12, 58. 574 A. Akaike, H. Katsuki and T. Kume, Endogenous Factors Regulating Neuronal Apoptosis, Nippon Shinkei, Seishin Yakurigaku Zasshi, 2005, 25, 245. 575 T. Akasaka and S. Nagase, Structure Elucidation of Endohedral Metallofullerenes, Kagaku (Kyoto, Jpn.), 2005, 60, 68. 576 H. Akutsu, Liposome Research by NMR, in Riposomu Oyo no Shintenkai, ed. K. Akiyoshi and K. Tsujii, Enu-Ti-Esu, Tokyo, Japan, 2005, p. 90. 577 T. Asakura, Structure of ‘‘Bombyx Mori’’ Silk Fibroin before Spinning Using NMR, Sen’i Gakkaishi, 2004, 60, P543. 578 T. Erata, The Cellulose Society of Japan Award for 2003. Achievements: The Analysis of Crystal Structure of Native Cellulose by Solid State NMR, Cellul. Commun., 2004, 11, 111. 579 N. Fujii, Nuclear Magnetic Resonance Spectroscopy, Shikizai Kyokaishi, 2005, 78, 572. 580 S. Gasa and Y. Yachida, The Structural Analysis and Property of Modiﬁed Glycosphingolipids, Sapporo Igaku Zasshi, 2005, 74, 1. 581 Y. Haga, H. Sakai, T. Matsuda, Y. Tokunaga, T. Fujimoto, S. Kanbe, E. Yamaoto, A. Nakamura, R. E. Walstedt, H. Yasouka, K. Nakajima, Y. Arai, D. Aoki, Y. Honma,

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582 583 584 585 586 587 588 589 590 591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608 609 610 611

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612 M. Nagakura, Applied Chemistry of Oils and Fats for Coatings. 125, Yushi, 2005, 58, 81. 613 M. Nakahara, NMR Studies on Water and Aqueous Solution in Supercritical and HighPressure Conditions, Koatsuryoku no Kagaku to Gijutsu, 2005, 15, 224. 614 K. Nakano, T. Hiyama and K. Nozaki, Asymmetric Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide, Kobunshi Ronbunshu, 2005, 62, 167. 615 Y. Nishimura, Role for NMR in Structural Proteomics, Tanpakushitsu Kakusan Koso, 2005, 50, 853. 616 T. Oishi and M. Murata, Synthesis of Labeled Natural Products Aiming at Elucidating the Mode of Action, Kagaku Kogyo, 2004, 55, 604. 617 T. Okuchi, Diamond Anvil Cell NMR, Koatsuryoku no Kagaku to Gijutsu, 2005, 15, 324. 618 M. Onaka, T. Okachi and S. Imachi, Stable Storage and Reactivity Increment of Labile Chemical Species in Polar Nano Space of Zeolite, Zeoraito, 2005, 22, 101. 619 K. Osakada and M. Tanabe, Platinum and Palladium Complexes with Metal–Silicon Bonds. New Bonding, Structures, and Chemical Properties, Bull. Chem. Soc. Jpn., 2005, 78, 1887. 620 A. Shiino, Clinical Applications of Proton MR Spectroscopy, Saishin Igaku, 2005, 60, 1036. 621 H. Takaba, A. Yamamoto and S.-I. Nakao, Diﬀusion in Polycrystalline Zeolite Membranes Investigated by 1H PFG NMR, Zeoraito, 2005, 22, 29. 622 K. Takeuchi and I. Shimada, Structural Basis of the K+ Channel Inhibition by PoreBlocking Toxins, Revealed by NMR, Tanpakushitsu Kakusan Koso, 2005, 50, 1297. 623 K. Tatsumi, Nano-Structural and Electrochemical Characteristics of Low Crystalline Carbonaceous Material and Carbonized Non-Graphitizable Carbon as Anode of Secondary Lithium Battery, Tanso, 2005, 217, 115. 624 T. Terauchi and A. Ono, Analysis of Higher-Order Structure of Proteins Employing Stable Isotope Labeling Amino Acid, Kagaku to Kogyo (Tokyo, Jpn.), 2005, 58, 1426. 625 K. Teshima, M. Kusunoki and T. Hase, Dynamics of Redox State-Dependent Ferredoxin Structure and Electron-Transfer Complex Formation with Ferredoxin: NADP+ Reductase, Seibutsu Butsuri, 2005, 45, 253. 626 T. Torizawa, T. Terauchi, A. Ono and M. Kainosho, The SAIL Method: A New NMR Approach for Larger Proteins, Tanpakushitsu Kakusan Koso, 2005, 50, 1375. 627 H. Yagi and H. Akutsu, What Is the Driving Force for the Rotation of ATP Synthase F1?, Tanpakushitsu Kakusan Koso, 2005, 50, 1160. 628 S. Yamada, Conformation-Control and Stereoselective Reactions Using Cation–p Interactions, Yuki Gosei Kagaku Kyokaishi, 2005, 63, 339. 629 Y. Yamamoto, Quantum Physics II Interdisciplinary Fields between Physics and Engineering, Nippon Butsuri Gakkaishi, 2005, 60, 928. 630 M. Yamanaka, T. Amaya and J. Rebek, Jr, Dynamics of Supramolecular Capsules, Yuki Gosei Kagaku Kyokaishi, 2004, 62, 1218. 631 Y. Yamane, N. Kamiguchi, M. Matsui, S. Kuroki and I. Ando, Material Diﬀusion in Polymer Gel and Network Structure by High Magnetic Field Gradient NMR, Kobunshi Kako, 2004, 53, 338. 632 H. Yasuoka, Materials Physics with Electromagnetic Wave. Evolution of NMR and mSR in Material Science, Nippon Butsuri Gakkaishi, 2006, 61, 3. 633 S. Yokoyama, Large-Scale Structural Proteomics Project at RIKEN: Present and Future, Tanpakushitsu Kakusan Koso, 2005, 50, 836. 634 H. Yoshimizu, T. Suzuki and Y. Tsujita, Characterization of Polymers in the Solid State by 129Xe NMR Spectroscopy, Sen’i Gakkaishi, 2004, 60, P498. 635 W. Bocian and L. Kozerski, Use of Nuclear Magnetic Resonance Spectroscopy in Studies of Intermolecular Interactions of Organic Ligands and Biomolecules, Wiad. Chem., 2005, 59, 3. 636 E. Bortel, E. Witek, A. Kochanowski and M. Pazdro, Poly(vinylamine) as a Source of New possibilities for Development of Hydrophilic Polymers, Polimery (Warsaw, Pol.), 2005, 50, 491. 637 A. Ejchart, Nuclear Magnetic Resonance Spectroscopy in the Determination of Protein Structures, Kosmos (Krakow, Pol.), 2004, 53, 263. 638 A. Ejchart, NMR Strategies for Structure Determination of Proteins in Solution, Wiad. Chem., 2005, 59, 23. 639 Z. Gdaniec, NMR Spectroscopy in Structural Studies of Nucleic Acids. Part I, Wiad. Chem., 2005, 59, 47. 640 A. Gryﬀ-Keller, Diﬀerentiation of Molecular Structure Using NMR Spectroscopy in Liquids, Wiad. Chem., 2005, 59, 67. 641 E. Halasa, Synthesis of Polyimides from Poly(Amic Acids) and Their Ester, Polimery (Warsaw, Pol.), 2005, 50, 20.

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642 S. Jankowski, NMR Spectroscopic Study of the Dynamics of Systems, Wiad. Chem., 2005, 59, 93. 643 W. Kozminski, Basic Experimental Techniques of NMR Spectroscopy in Liquids, Wiad. Chem., 2005, 59, 10. 644 A. Nonat, The Structure of C–S–H, Cem.–Wapno–Beton, 2005, 10, 65. 645 A. Pawlak, Sound Propagation Near the Magnetic Phase Transition, Ser. Fiz. (Uniw. im. Adama Mickiewicza Poznaniu), 2004, 80, 1. 646 A. Plichta, Z. Florjanczyk and G. Rokicki, Cyclic Carbonates in the Synthesis of Biodegradable Polymers, Polimery (Warsaw, Pol.), 2005, 50, 537. 647 W. M. Rzymski, A. Cebulski, S. M. Jachna and P. Ogieglo, Determination of Bound Styrene in Butadiene-Styrene Rubber and in Other Styrene Copolymers, Przem. Chem., 2005, 84, 646. 648 K. W. Szewczyk, Mathematical Models in Metabolic Engineering, Biotechnologia, 2005, 2, 7. 649 E. Tylek, J. Polaczek and J. Pielichowski, Methods for Analysis of Poly(aspartic acid) and Its Derivatives, Polimery (Warsaw, Pol.), 2005, 50, 341. 650 I. Wawer, M. Pisklak and K. Paradowska, Pharmaceutical and Medical Diagnostic Applications of Solid-State NMR, Wiad. Chem., 2005, 59, 12. 651 D. N. Akbaeva, Organometallic Complexes of Transition Metals Containing a P4 Molecule as a Monohapto-Ligand, Izv. Nats. Akad. Nauk Resp. Kaz., Ser. Khim., 2005, 2, 66. 652 M. I. Makarov, Phosphorus-Containing Components of Soil Organic Matter: 31P NMR Spectroscopic Study (A Review), Pochvovedenie, 2005, 2, 172. 653 N. A. Semenova, The Method of NMR Spectroscopy forStudying in vivo Metabolic Processes. Details of Energy Metabolism in Brain Evaluated from NMR in vivo, Usp. Sovrem. Biol., 2005, 125, 419. 654 A. Fedurcova, J. Lehotay and J. Cizmaric, Interconvention of Stereochemically Unstable Chiral Drugs: Utilization of Chromatographic Techniques for the Study of Enantiomerization. Part II: Practical Applications, Ceska Slov. Farm., 2006, 55, 12. 655 A. Alvarez, D. Muniz, F. Riera, R. Alvarez and C. Menendez, Stability of Milk Proteins: Immunoglobulins. Basic Characteristics and Techniques for Their Activity Determination, Aliment., Equipos Tecnol., 2005, 199, 68. 656 A. Munoz Bonilla and M. Fernandez-Garcia, Polymeric Molecular Imprinting. II Characterization and Applications, Rev. Plast. Mod., 2005, 90, 67.

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Theoretical and physical aspects of nuclear shielding Cynthia J. Jamesona and Angel C. de Diosb DOI: 10.1039/b618338g

1. Theoretical aspects of nuclear shielding 1.1 General theory Relativistic eﬀects on molecular magnetic properties, in particular the nuclear magnetic shielding tensor, can be signiﬁcant in molecules containing heavy atoms. Many approaches have been put forward. One approach is to append the spin–orbit interaction to the non-relativistic theory. Nakatsuji et al. presented an ab initio UHF formalism for calculating the spin–orbit (SO) eﬀect without electron correlation1 and applied it to many systems,2–5 while Malkin et al. presented a density functional theory (DFT) formalism,6 and Vaara et al., on the other hand, used multi-conﬁguration self consistent ﬁeld (MCSCF).7,8 While these works showed the importance of including the spin orbit eﬀects, particularly to understanding the observed ‘‘normal halogen dependence’’, this approach clearly is insuﬃcient for the nuclear shielding of heavy nuclei. Several methods have been proposed to reduce the fourcomponent Dirac equation to two-component equations. The most successful twocomponent relativistic method to date starts with the no-pair formalism and external ﬁeld projectors, as developed by Douglas and Kroll and Hess. Nakatsuji and coworkers used a two-component quasi-relativistic (QR) theory based on the DouglasKroll-Hess transformation,9,10 included the change of picture eﬀect which ensures consistency with the Hellmann-Feynman theorem for the QR theory,9 adopted gauge-including atomic orbitals (GIAO) method for gauge origins,10 and incorporated electron correlation at the MP2 level in this reporting period.11 Fukui and Baba developed a two-component method that derived the expression for the nuclear shielding from the Douglas-Kroll-Hess (DKH) transformation of the nopair equation for a molecule bearing a nuclear moment and is placed in a magnetic ﬁeld; they used common origin coupled Hartree–Fock to begin with,12 later introduced GIAOs.13,14 In these earlier works, the ﬁnite perturbation method was used to compute nuclear shielding values. In this reporting period, Kudo and Fukui derived expressions for the shielding tensor by analytically diﬀerentiating the electronic energy of a system based on the Douglas-Kroll-Hess approach.15 Earlier, Fukui, Baba and Inomata had derived a two-component formalism using the Breit-Pauli approach; the magnetic vector potential is added to the canonical momentum in the Breit-Pauli Hamiltonian in order to get a gauge-invariant scheme up to order c4.16,17 In the process, a mass correction term in the shielding became apparent for the ﬁrst time, arising from a second order expression containing the Fermi contact terms and the kinetic energy operators. The same approach was carried out more completely by Manninen et al., avoiding some of the approximations introduced by Fukui et al.18–20 Another alternative two-component approach to NMR properties begins with the zeroth order regular approximation (ZORA) Hamiltonian; an external magnetic ﬁeld and nuclear moment are introduced. Wolﬀ and Ziegler derived the equations for calculating the nuclear shielding tensor in the ZORA formulation and implemented them within an existing density functional program for which the ZORA a b

University of lllinois at Chicago, Department of Chemistry, 845 W, Taylor Street, Chicago, IL, 60607-7061, USA Department of Chemistry, Georgetown University, Washington, DC, 20057-2222, USA

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part had already been developed by van Lenthe et al.21 This version of the twocomponent approach has been applied to many molecular systems involving heavy atoms by Ziegler and others.21–24 Fukui et al. have also derived a ZORA version, but without electron correlation.25 A third approach which leads to a two-component method of calculating nuclear shielding is the linear response within the elimination of small components (LR-ESC), introduced by Melo et al.26 They start with a four-component Rayleigh-Schrodinger perturbation theory formalism, and construct a two-component theory by using the elimination of small component scheme, thereby obtaining formal expressions for operators previously neglected.26 They arrive at expressions similar to Fukui et al.16,17 plus some additional terms correcting both the diamagnetic and paramagnetic parts of the shielding. Thus, the formal relation between the Breit-Pauli approach of Fukui et al. and the LR-ESC approach of Melo et al. had been shown.26 Yet another formalism is Kutzelnigg’s minimal coupling approach.27 He developed two-component expressions of magnetic properties starting from the Dirac equation in the presence of a magnetic ﬁeld and using direct perturbation theory. By carrying out a double perturbation expansion (in c1 and in the magnetic vector potential) he arrived at formal perturbative expressions based on the Levy-Leblond Hamiltonian.27 Are these two-component approaches equivalent to each other? It is diﬃcult to ascertain the answer to this question, in part because basis set incompleteness errors do not impact contributions in diﬀerent approaches uniformly and in part because two-body contributions which are diﬃcult to calculate are sometimes not included. A full four-component treatment is to adapt Ramsey’s theory to the fourcomponent Dirac equation. In a four-component context all relativistic corrections are included from the beginning.28,29 Within the random phase approximation (RPA) method, four-component relativistic calculations of nuclear shielding have been derived by Visscher et al.30 Four-component calculations have been carried out on small molecular systems.19,28–33 where it should be noted that refs. 30 and 31 have an error in having neglected positronic excitations in RPA calculations and refs. 28, 32 and 33 have used modest basis sets. It seems natural to identify the paramagnetic contribution as that originating in operators linear in the magnetic vector potential A, and to identify the diamagnetic contribution as that from operators linear in A. With this deﬁnition, various approaches to the calculations of relativistic eﬀects on nuclear magnetic shielding yield diﬀerent decompositions into para- and diamagnetic components of magnetic properties. There are diﬀerent deﬁnitions of para- and diamagnetic contributions at the four component level yielding the same para- and diamagnetic separation in the non-relativistic limit. In a very useful paper in this reporting period, Zaccari et al.34 attempts to clear up the situation by analyzing the formal relations connecting the diﬀerent para- and diamagnetic contributions of three approaches: the Breit-Pauli, the LR-ESC, and the minimal coupling approaches, as they were presented in refs. 19, 26 and 27, respectively. In the process, the equivalence of these three approaches within the elimination of the small component approximation is proven and veriﬁed numerically for the HX series of molecules (X ¼ Br, I). Formal relations are presented proving the gauge origin invariance of the full relativistic eﬀect on the nuclear shielding tensor within the LR-ESC approach. Only one-body terms are included in the analysis by Zaccari et al.34 Finally, these three equivalent approaches, represented by the Breit-Pauli approach,20 can be compared to the Douglas-Kroll Hess,15 and three other twocomponent methods, and also with the non-relativistic values and the benchmark full 4-component Dirac-Fock with an analytical linear response approach.19,29 Table 1 is a comparison of the calculated results for the isotropic nuclear shieldings for noble gas atoms, HX (X ¼ F, Cl, Br, I), and H2X (X ¼ O, S, Se, Te) molecules. Presented in Table 2 are the anisotropies of the shielding in HX (X ¼ F, Cl, Br, I), and H2X (X ¼ O, S, Se, Te) molecules. Kudo and Fukui also developed a second Nucl. Magn. Reson., 2007, 36, 50–71 | 51 This journal is

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Table 1 Calculated results for isotropic nuclear magnetic shieldings (in ppm) for noble gas atoms (Ne to Xe), HX (X ¼ F, Cl, Br, I), and H2X (X ¼ O, S, Se, Te) molecules. All calculations are at the Hartree–Fock level

O in H2O S in H2S Se in H2Se Te in H2Te F in HF Cl in HCl Br in HBr I in HI H in HF H in HCl H in HBr H in HI Ne Ar Kr Xe

NonRel15

4-component DHF19,29

BreitPauli20

Douglas-KrollHess15

IOTCCHF15

NESCZORA36

NESCSORA36

327.7 719.2 2153.4 3463.5 412.0 953.1 2615.9 4752.4 26.72 30.05 29.70 35.33 551.5 1237.7 3234.7 5590.7

330.7 738.3 2441.4 4806.7 418.4 984.5 2959.4 5913.7 28.03 31.18 35.86 47.05 561.3 1274.3 3579.5 6965.2

330.8 737.3 2406.2 4569.4 418.1 977.1 2922.0 5598.2 28.60 31.78 36.93 50.65 556.6 1273.3 3553.8 6718.5

331.1 747.0 2463.2 4668.4 417.1 988.3 2982.1 6303.4 26.92 30.51 35.45 44.18 558.3 1280.3 3631.8 7177.9

331.1 746.6 2454.8 4626.5 417.0 987.8 2972.2 6245.0 26.92 30.51 35.46 44.20 558.3 1279.7 3621.1 7120.6

421.0 994.4 3011.5 5924.5 28.17 31.37 36.10 48.11

421.0 994.3 3023.3 6192.4 28.17 31.37 36.10 48.08

expression based on the method of Barysz-Sadlej-Snijders, in which the oﬀ-diagonal block terms in the transformed Dirac Hamiltonian are completely eliminated with respect to purely electrostatic nuclear attraction potential and the magnetic vector potential A. This is an inﬁnite order two-component DKH method (IOTC). They carried out calculations using the same basis sets for the same molecular systems,15 and these results are included in Tables 1 and 2 with the label IOTC. In addition to these two-component methods already discussed above, Filatov and Cremer35 recently introduced a normalized elimination of small component (NESC) method which Kudo et al. have extended to include magnetic interactions.36 Filatov and Cremer have developed the regular approximation to the normalized elimination of the small component (NESC) to the Dirac equation and this was used as a starting point for the development of a second order regular approximation to NESC, with the acronym NESC-SORA. The NESC method corresponds to the projection of the Dirac Hamiltonian onto a set of positive-energy (electronic) states, which guarantees its variational stability. NESC-ZORA and NESC-SORA can easily be implemented in any non-relativistic quantum mechanical program. Both methods have been applied by Kudo et al. to the same set of molecular systems and these results are compared with the other methods in Tables 1 and 2. Incidentally, what is typically called ZORA is the lowest order regular approximation to the equation for the unnormalized elimination of the small component. We note that of the two-component methods, those which gave the best agreement with the benchmark four-component calculations are the IOTC, NESC-ZORA and NESC-SORA methods. The Breit-Pauli, which has been shown to be formally analytically equivalent to the LR-ESC, gives a poorer result for the full shielding tensor, as shown by the too large anisotropies of I in HI and Te in H2Te, for example. The Douglas-Kroll-Hess fails to give a good account of the anisotropy of the shielding of both I and H nuclei in the HI molecule. The last three columns in Tables 1 and 2 seem to indicate that the two component methods can give results which are reasonably close to the four-component calculations. These are all largebasis-set calculations which do not include electron correlation. Correlated relativistic calculations are, so far, available in the form of DFTZORA21 and the recently introduced DKH-MP2 by Fukuda and Nakatsuji.11 The latter has been applied to Te shielding calculations, using only modest basis sets, 52 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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Table 2 Calculated results for the anisotropy of nuclear magnetic shieldings (in ppm) for HX (X ¼ F, Cl, Br, I), and H2X (X ¼ O, S, Se, Te) molecules. All calculations are at the Hartree– Fock level. Ds ¼ s8 s> for HX molecules, and Ds ¼ s33 (s11 þ s22)/2 for H2X molecules

O in H2O S in H2S Se in H2Se Te in H2Te F in HF Cl in HCl Br in HBr I in HI H in HF H in HCl H in HBr H in HI

NonRel15

4-component DHF19,20

BreitPauli20

Douglas-KrollHess15

IOTC15

NESCZORA36

NESCSORA36

58.0 319.6 685.7 1463.0 100.3 287.2 722.6 872.9 24.28 21.73 28.19 42.75

57.1 317.1 668.5 1232.4 100.7 288.2 664.0 1025.2 23.80 21.32 18.11 0.39

57.8 317.5 747.9 1692.1 103.1 408.5 792.6 1627.1 23.14 20.51 17.45 1.21

58.6 317.4 659.4 1216.0 98.9 285.6 641.4 651.2 23.96 20.85 18.60 26.57

57.8 317.3 658.4 1212.6 99.0 285.7 641.7 981.0 23.96 20.85 18.59 2.18

99.0 286.7 647.8 1033.5 23.80 20.97 17.93 3.19

99.0 286.7 647.8 1033.9 23.80 20.97 17.93 3.20

however, and it is not clear whether all relativistic terms have been included. For example, the non-relativistic and DKH isotropic shielding values calculated for Te in H2Te were, respectively 3644 and 5094 ppm11 which can be compared to the values 3463.5 and 4569.4 ppm in the Table 1. There have been other correlated relativistic calculations such as those using MCSCF functions, but which only included spin orbit contributions.7,8 A new two-component method has been developed which solves the Dirac equation at the Kohn–Sham level of theory using a basis for the large component only and avoids some of the approximations used in the standard ZORA method.37 This is related to the widely used ZORA approach in that it is an unnormalized elimination of small component method, and that it is density functional theory based rather than ab initio. This new approach, labeled DKS2RI (Dirac-Kohn–Sham with resolution of identity approximation), employs the resolution of identity approach to reformulate the basic Dirac-Kohn–Sham equations before elimination of the small component. No picture-change problems arise in electronic property calculations by this method. The ﬁrst applications of the method are to calculations of hyperﬁne constants for atoms. The diﬀerences between ZORA and this method are small for Cu and Ag and larger for Au: 6750 vs. 6737; 1909 vs. 1967; and 3134 vs. 2986 all in MHz for ZORA vs. DKS2-RI methods, respectively.37 The method has also been applied to calculations of hyperﬁne constants of Hg in HgH, HgF and HgCN. The new DKS2-RI method gives uniformly smaller values than ZORA, and the agreement with experiment is worse for DKS2-RI, except in the case of HgH and Au. Spin–orbit contributions to the hyperﬁne tensor can be substantial and in the examples calculated to date, it looks like they tend to decrease the magnitude of the isotropic contact hyperﬁne, while the dipolar part of the hyperﬁne tensor remains the same. DFT calculations of the 13C hyperﬁne tensors in metallocenes with and without inclusion of spin–orbit contributions reveal that, depending on the metal atom, the calculated 13C contact hyperﬁne is 74 to 84% of that obtained without including SO.38 In a particular nitroxide radical where both signs of contact hyperﬁne are observed, the magnitudes of the 13C contact hyperﬁne of the eight inequivalent carbons are all smaller when SO is included in the calculations. As discussed in vol. 34 of this series, the remarkable experimental values of the shielding tensors measured for the XeF2 molecule23 provide the clear indication that insights we have derived from mathematical identities which relate one molecular electronic property to another based on non-relativistic Hamiltonians are completely overturned in systems involving very heavy atoms, since the same identities do not Nucl. Magn. Reson., 2007, 36, 50–71 | 53 This journal is

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hold in the relativistic case. The DFT-ZORA calculations which accompanied the experimental report gave anisotropies of 4469 ppm and 277 ppm for Xe and F nuclei.23 A recent IOTC-CHF (see above for description of this method) calculation by Kudo et al.39 gave 4276 and 115 ppm, which can be compared with the experimental values 4245 ppm and 150 ppm, respectively. The isotropic shielding values for Xe and F nuclei are, respectively, 3007 and 339 ppm from DFT-ZORA while they are 3570 and 415 ppm from IOTC-CHF. Diﬀerences may be due to neglect of electron correlation in the one case and the real diﬀerences between t he unnormalized elimination of small component ZORA method compared to the inﬁnite order two component formalism based on the Barysz-Sadlej-Snijders method. The search for better approximations to exchange correlation functionals for use in DFT calculations continues in this reporting period. What is the optimum admixture of exact exchange? To ﬁnd this, hybrids, such as Becke3, have been parametrized on sets of thermochemical data, properties which are directly associated with the total energy.40 On the other hand, it has been found that relatively large admixtures of exact exchange give better values in shielding calculations.41 Another approach is to convert non-local and non-multiplicative hybrid exchange– correlation potentials into local and multiplicative Kohn–Sham potentials. To do this, Wilson and Tozer used the iterative approach of Zhao, Morrison and Parr (ZMP),42 to convert a given electron density to a multiplicative KS potential, which was then applied to the calculation of nuclear shieldings.41 The advantage of this method is that electron densities derived from any, even non-DFT methods, can be used as the starting point. On the other hand, instead of this ZMP approach, Arbuznikov and Kaupp43–45 construct the Kohn–Sham potential by applying the socalled localized Hartree–Fock approximation to the optimized eﬀective potential method.46 The resulting localized hybrid exchange–correlation potentials provide improved performance at very nearly the same amounts of admixture of exact exchange (close to 0.5) and nearly independent of which standard DFT functional is used (LYP, or PW91, or PBE).44,45 These conclusions are based on results for nuclear shielding in 22 light main-group molecules. Furthermore, they ﬁnd that an adaptable formulation of local hybrid functionals with position-dependent exact exchange admixture enhances ﬂexibility. At every point in space, a local mixing function determines the amount of exact exchange admixture.47 This has been tested with thermochemical properties but remains to be tried on shielding calculations. Actually, the concept of position-dependent local mixing functions had been proposed ﬁrst by Becke when he proposed his hybrid functionals.40,48 The performance of CAM-B3LYP, a hybrid exchange correlation energy functional based on the Coulomb-attenuating method (CAM), is compared with standard B3LYP.49 While it gives improvement in long-range properties, for isotropic nuclear shielding the results are comparable to B3LYP. It has been demonstrated with self-consistent ﬁeld calculations that the basis-set dependence of magnetic properties can be characterized by a parameter t, that describes the deviation of the basis set from completeness in the exponent range (which corresponds to distance from the nucleus) relevant for the property of interest.50 The completeness proﬁle concept introduced by Chong51 is particularly useful for molecular properties that may be dominated by phenomena occurring close to atomic nuclei, which are then best described by high-exponent basis functions, or for those dominated by the valence regions farther away from nuclei, which are best described by diﬀuse basis functions. Based on this a scheme for designing Gaussian-type orbital basis sets is proposed. Instead of optimizing the parameters of the basis sets with respect to electronic energy, a primitive set is constructed at the outset so as to be complete for a range of exponents relevant for the speciﬁc property. This has been illustrated for nuclear shielding;50 completeness proﬁles of existing basis sets and code for generating completeness-optimized basis sets are made available at http://www.chem.helsinki.ﬁ/Bmanninen/kruununhaka. 54 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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NMR can distinguish diastereomers but conventional NMR spectroscopy is blind to a full mirror image; that is, it is unable to distinguish between the two mirrorimage forms of a chiral molecule. It has been shown that the shielding tensors for the left and right-handed enantiomers are identical except for the antisymmetric parts, whose oﬀ-diagonal components diﬀer only in sign. Nevertheless, A. D. Buckingham has shown that52 in principle, chirality may be directly observable in NMR spectroscopy without the need for a chiral auxiliary, although not in conventional NMR spectroscopy. The manifestation of chirality in the chemical shift can be proved using simple symmetry arguments.53 The eﬀective Hamiltonian for nuclear spins can be obtained from the ground state energy of the electronic and nuclear system in which they are embedded. This energy must be time even and an overall scalar. In the presence of a static electric ﬁeld E, static magnetic ﬁeld B, and nuclear spin operator S, for an isotropic system the only scalar that may be formed from these three vectors is a pseudoscalar, PS ¼ S . B E, which is time even. Hence the contribution to the ground state energy may be written as EG ¼ s S . B þ schiral S . B E, Under parity, EG is unchanged; however, schiral goes into-schiral, so schiral must be a pseudoscalar. Hence the chiral portion of the chemical shift for each enantiomer is schiral for the left-handed enantiomer and—schiral for the right-handed enantiomer. Buckingham and Fischer54 suggest three experiments which can lead to observables only for chiral molecules. A laser polarized in the plane perpendicular to the ﬁeld of the magnet may in principle give rise to chiral chemical shifts. The coherent precession of nuclear spins following application of a p/2 pulse to an optically active liquid will lead to a rotating macroscopic electric polarization. In a chiral liquid, the application of an oscillating electric ﬁeld at right angles to the magnetic ﬁeld of the spectrometer may give rise to a magnetization oscillating at a unique frequency in the direction of the permanent magnetic ﬁeld. Of course NMR without electric ﬁelds, without diastereomers, is not totally blind to chirality. Parity is not conserved, so there is a tiny pseudoscalar component to the shielding.55,56 In this reporting period, parity violation eﬀects in the nuclear magnetic shielding are evaluated using analytical linear-response theory in the framework of the Breit-Pauli Hamiltonian, based on Hartree–Fock and DFT reference states.57 The calculated splitting in the 19F NMR spectrum between the left and right-handed CHFClBr molecules in vacuum is 2.34 1010 ppm (using Hartree–Fock) or 3.52 1010 ppm (using DFT-B3LYP). The order of magnitude of these eﬀects is in agreement with earlier estimates.58,59 1.2 Ab initio and DFT calculations Calculations of shielding tensors for heavy nuclei such as 183W and 129Xe require relativistic treatment,39,60,61 as do nuclei having neighbors which are heavy atoms, such as 19F in XeF2,39 and in uranium complexes,62 17O in polyoxotungstates,60,61 31P and 15N in a lead (II) complex,63 and the interstitial 13C in an octahedral gold cluster.64 The XeF2 molecule has been discussed above. DFT-ZORA calculations of 183W and 17 O shielding in polyoxotungstate ions having as many as 18 W atoms in the cluster have been carried out.60,61 Relativistic core potentials were used for the internal or core electrons and Slater-type orbitals (STO) for the rest. The valence orbitals are kept orthogonal to the core orbitals by means of a single-z Slater type coreorthogonalization basis set. Optimization of structure results in a unique conﬁguration of a cluster anion. Solvation eﬀects are not included. A linear correlation of calculated and experimental values of chemical shifts for 17O gives a slope of 1.0623, Nucl. Magn. Reson., 2007, 36, 50–71 | 55 This journal is

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but for 183W shifts the best-ﬁt line has a slope of 0.7854, although both have R2 better than 0.98. The calculated 183W shifts permit assignments of non-equivalent W nuclei, albeit the calculated chemical shift range is substantially expanded compared to experiment. The 17O chemical shift range is well-reproduced by the calculations. The relationships between structure and chemical shift are discussed, and the calculations provide a means of understanding the nature of the bonding in these clusters. The 19F shielding in the uranium complexes UFnCl6n have previously been calculated by all-electron ZORA and Pauli methods by Schreckenbach.65,66 In this reporting period, DFT calculations were carried out with various functionals using a relativistic small core pseudopotential on uranium.62 These authors claim that the DFT results can be of comparable quality to those obtained previously by relativistic calculations; instead of the usual eﬀective core potentials, they recommend using a small inner core. However, there is large dependence on the type of functional used. There is only a 40.3 ppm range in the experimental chemical shifts for all nonequivalent 19F sites, while there is a 124 ppm range for one 19F site (UF6) in the DFT-calculated values, depending on which functional is used. The interstitial 13C in an octahedral gold cluster is in a unique bonding situation, surrounded by six Au atoms having phosphine-type ligands.64 The 13C nuclei in interstitial transition metal carbides are known experimentally to be greatly deshielded, with chemical shifts as large as 450 ppm, for example. On the other hand the 183W nucleus in the WAu12 cluster is greatly shielded. DFT-ZORA calculations ﬁnd the interstitial carbon in an octahedral gold cluster [(Ph3PAu)6C]21 to have a chemical shift of 99.6 to 128.7 ppm relative to TMS, depending on the functional and basis set used. The experimental value is 135.2 ppm. The strongly shielding spin–orbit contribution from the Au cage is suppressed due to electronic eﬀects from the phosphine ligands. Without the phosphine ligands the calculated chemical shift is around 300 ppm.64 All-electron DFT-ZORA calculations, including spin–orbit coupling, of 119Sn in SnH4, Me4Sn, Me4n SnXn (X ¼ Cl, Br, I, n ¼ 1 3) and SnH31 (stannyl cation) ﬁnd that calculated shifts correlate well with experimental values only when spin orbit terms are included.67 The observed chemical shift of the stannyl cation does not correspond to a bare cation but rather one that is strongly coordinated to a partner such as FSO3H. 99Ru shielding calculations at the DFT level using B3PW91 hybrid functional and small basis sets (3-21G* on Ru and 6-21G* on all other atoms) correlate well (one could say fortuitously) with experimental chemical shifts.68 DFT calculations of 77Se shielding were carried out using B3LYP and GIAO with basis sets 6-311þG(3df) for Se and 6-311þG(3d,2p) for other nuclei in order to understand the relationship of the chemical shift to the orientation of the Aryl group in ArSeR (RQH, Me, Ph) compounds, where Ar ¼ p-YC6H4, (Y ¼ COOEt, CN, NO2).69 It would have been more enlightening to have looked at the full tensor instead of just the isotropic value. Nevertheless, the authors found that a molecular orbital analysis of the contributions to the Se shielding was helpful in understanding the orientation dependence. Phosphorus shielding has been investigated in phosphoranes,70 in the reference liquid, concentrated phosphoric acid.71 chiral phosphorus sulﬁde cages,72 and bimetallic diphenylphosphinopyridine compexes where the metals are Ru and either Zn, Cd, or Hg.73 It has been known experimentally that phosphoranes, with rare exceptions, have chemical shifts well upﬁeld of the common reference 85% phosphoric acid, mostly in the range d ¼ 50 to 100 ppm, and this generalization has been employed in many cases to decide if a structure is truly a phosphorane, or is the 4-coordinate phosphonium ion (with positive shifts of d ¼ þ15 to þ20 ppm). Chesnut has been using his estimated inﬁnite order Møller–Plesset and scaled DFT for several systems, with reasonable success. In this work, he also employed the conductor like solvaton model (COSMO) to take care of solvent eﬀects in aqueous solution and ﬁnds a good correlation with experiment except for multiple chloro compounds, (which should of course be treated relativistically, at least to include the spin–orbit contributions).70 The calculation of the shielding of a liquid reference 56 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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compound is particularly problematic in the case of 31P, because many ionic and molecular species are in equilibrium with each other in a polyprotic acid such as phosphoric acid. Chesnut considered clusters which are hydrated versions of these species, at optimized geometries with one or two waters, as well as dimers and trimers of H3PO4.71 Solutions of naturally occurring phosphates, while occurring in an equilibrium mixture of undissociated, partially dissociated, and completely dissociated species nevertheless span a narrow chemical shift range of 0.1 to 2.6 ppm. Calculations of gas phase species, even hydrated ones, give a much larger range which is about one order of magnitude larger. So it remains an open question what gives rise to the narrow chemical shift range. Perhaps, there is fast exchange between the various species so that calculations of individual static species cannot duplicate experimental observations. The calculations in the bimetallic complexes are not particularly convincing, since the experimental range for the three compounds is only 11 ppm and the errors in the shielding calculations when the method gives optimized bond lengths which are in error by more than 0.1 A˚.73 The 31P calculations in the diastereomers of closo-derivatives of P4S3 cages point towards absolute conﬁgurations, but since many rotamers are possible and the diastereomeric shift is not large, assignment of conﬁguration by computations is not certain.72 29 Si shielding in disilynes have been analyzed in terms of the MO contributions.74 17 O shielding in crystalline tellurites do not depend on whether the oxygen is at a bridging or non-bridging position.75,76 This is very surprising since the two sites diﬀer formally by a full electronic charge, and is in contrast to the clear diﬀerences observed in the case of silicates. An understanding of this similarity in shielding is gained by a study using plane waves and pseudopotentials.76 11B chemical shifts have been calculated in various compounds using DFT-GIAO methods.77–79 In the case of halogen-substituted compounds, the spin–orbit contribution needs to be included.77 A systematic study of basis sets in reproducing by Hartree–Fock and DFT-B3LYP calculations the experimental 13C shielding tensors obtained from single crystal experiments included 102 tensors from 14 organic crystals and examined 81 combinations of basis functions.80 The correlation between calculated and experimental values is perfect when the slope is unity and the intercept is consistent with the deduced absolute shielding of liquid TMS. The calculations did not include vibrational averaging or neighbor eﬀects, The general ﬁndings are as follows: (a) Hartree–Fock leads to consistently too shielded values, whereas DFTB3LYP leads to consistently too deshielded values. It had previously been found that aromatic carbon shielding tensors are particularly sensitive to the technique used to describe electron correlation. This is borne out in this study. (b) The intercept for Hartree–Fock is consistently 20 ppm higher, consistent with the sign of the electron correlation contribution. (c) The slope is particularly sensitive to the description of the valence region. A large increase is observed going from the ‘21’ split valence to the ‘31’ as well as to the ‘311’ valence triple zeta. This increase leads toward better overall results in the DFT method. (d) Going from double to triple to quadruple zeta using the Hartree–Fock method leads to apparently worse slope. There is a mix of carbon chemical sites in the systems studied; the sites which have larger electron correlation contributions are at the ones which appear at the least shielded end of the range of experimental values. Not including electron correlation therefore leads to the wrong slope. (d) A balance between the polarization added to both heavy atoms and hydrogens must be kept. (e) At least one d function on the heavy atoms must be included to obtain good slope values as well as acceptable rmsd values. (f) Diﬀuse functions have less of an impact than polarization functions. The r3 in the operators leads to greater sensitivity to the description close to the nucleus, whereas diﬀuse functions extend further in space. For this aspect, Chong’s completeness proﬁle concept,51 discussed above, would be useful. The basis-set dependence of magnetic properties can be characterized by the parameter t which describes the deviation of the basis set from completeness in the exponent range (which corresponds to distance from the nucleus) relevant for the property of interest; Manninen et al. Nucl. Magn. Reson., 2007, 36, 50–71 | 57 This journal is

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have applied Chong’s concept to testing basis sets for nuclear shielding calculations.50 The study by Sefzik et al.80 was a very useful study in that the quality of the data from single crystal experiments is very high and consistently from the same highly expert laboratory, the full tensor information was available for comparisons, the availability of X-ray data meant that the geometries used in the calculations were reliable. There is the remaining problem that since the calculations did not include neighbor eﬀects, the missing ring current contributions and hydrogen bonding eﬀects which diﬀerentially impact the accuracy of the calculations for aromatic carbons and the saccharides, respectively, could aﬀect the validity of the conclusions. DFT/GIAO Calculations of 13C shielding in particular compounds have been used (a) to assign the experimental peaks in several studies, such as for free-base porphine, porphyrazine, phthalocyanin and napththalocyanin and their metal complexes,81 (3aminopropyl)guanidine and (trans-4-aminocycloexyl)guanidine,82 N-substituted pyrazoles and indazoles,83 a cycloheptenone derivative,84 substituted 3-nitropyridines,85 chloropyrimidines,86 (b) to assign the structure of newly isolated metabolites from marine animals,87 of benzothiazepines and benzothiazines,88 of hexacyclinol,89 of the products of condensation of hydroxylamine with triﬂuoromethyl-b-diketones,90 of some new 4-heteroarylidenamino-4,5-dihydro-1H-1,2,4-triazol-5-one derivatives,91,92 (c) to ﬁnd the preferred conformers of chlorobornenes in solution,93 of the bicyclic pheromone from a beetle,94 (d) to distinguish between macrocyclic ligands, the smaller and larger sized cucurbit[n]urils, (n ¼ 5 to 8),95 (e) to investigate the changes to the principal components of the shielding tensor upon N-oxidation of quinolines which are anti-malarial drugs,96 (f) to study the inﬂuence of axial or equatorial Br substitution on 13C chemical shifts in spirostanes and furostanes,97 (g) to study the dependence of the shielding on the angle between the planes of the two aromatic or heteroaromatic rings in Tro¨ger’s bases,98 and (h) to study the equilibrium between tautomers of triketones 2-acylcyclohexane-1,3-diones.99 1.3 Semi-empirical calculations A review of prediction of chemical shifts using semi-empirical models, with particular applications to the 1H chemical shifts in proteins has appeared.100 The isotropic chemical shift is considered to be a sum of through-bond and through space contributions, with the through space contributions including the electric ﬁeld eﬀects, magnetic anisotropy eﬀects, ring-current eﬀects, and solvent eﬀects.

2. Physical aspects of nuclear shielding 2.1 Anisotropy of the shielding tensor We begin this section by citing the single crystal studies of peptide 15N shielding tensors by Waddell et al. 101 These studies focus on the central peptide (Gly and Pro) in three tripeptides GGV, AGG and APG. In all cases, the least shielded component s11 of the tensor 15N shielding is found to lie about 20–231 from the N–H vector in Gly and from the N–Cd bond in Pro. In addition, the s22 component, which is usually assumed to be normal to the amide plane, is observed to deviate from this orientation. These results are in general agreement with previous experimental powder-NMR studies 102 and predictions from theoretical work.103 The recent work likewise explores theoretical calculations and found, that in DFT calculations, results on amide 15N shielding tensors, obtained with 6-311þþG(d,p) are already comparable to those of a larger basis set (aug-cc-pv5z). In accordance with earlier tensor calculations in hydrogen-bonded systems, the use of dimer and trimer clusters, which incorporate hydrogen bond partners, is shown to be important in quantitatively predicting the orientation of the 15N shielding tensor. Wylie et al.104 have determined the 15N shielding anisotropy in the solid state for 51 backbone amide sites of the 56-residue b1 immunoglobulin binding domain of protein G 58 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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(GB1). By employing the recoupling of chemical shift anisotropy (ROCSA) method developed by Chan and Tycko,105 combined with speciﬁc polarization transfer to either 13Ca or C0,106 3D 15N–15N–13C sets of data have been collected, from which amide 15N shielding tensor data could be extracted. The new shielding tensor data reveal that 15N sites in a-helical segments of a protein have a higher anisotropy (by about 6 ppm) compared to those in b-sheet regions. 13 C shielding tensor measurements continue to play a signiﬁcant role in the elucidation of structures and dynamics of biologically relevant molecules. Ying et al.107 have measured the 13C shielding anisotropy in DNA bases by taking advantage of NMR relaxation rates measured at two diﬀerent magnetic ﬁelds (500 and 800 MHz proton frequency). In a related study, Hansen and Al-Hashimi have shown that incorporation of residual chemical shift anisotropy of 13C sites in nucleobase carbons in a weakly aligned stem-loop RNA provides additional restraints for structure determination.108 Recoupling of anisotropy information (RAI) 109 has also been applied to the solid state NMR study of Bombyx mori silk ﬁbroin protein.110 Lastly, Hall and Fushman111 have used a combination of relaxation and cross-correlation measurements at ﬁve diﬀerent magnetic ﬁelds to measure the amide 15N shielding tensors in protein G in solution. Their ﬁndings of a signiﬁcant variability in the 15N shielding tensor throughout the protein illustrate the importance of using site speciﬁc 15N shielding tensors (instead of a uniform 15N shielding tensor for all residues) in analyzing protein dynamics from 15N relaxation measurements. The intimate relationship between electronic structure and the magnitude of shielding tensor components is once again illustrated in the work of Strohmeier et al.112 on tetracyanoethylene (TCNE) and its dianion, p-(TCNE)22. The dianion is formed via a 2.9 A˚ bond between the two monomeric units. The interaction between the monomers, expected to be a combination of Coulomb and van der Waals forces, as well as a singlet coupling of the two unpaired electrons of the monomer anions, is examined through the metric of the magnitudes of the principal components of the 13C shielding tensors in TCNE. The ethylenic C sites show dramatic changes upon dimer formation in their in-plane shielding components. These are the components that lie perpendicular to the line of approach between the two TCNE units. Likewise, similar changes are observed for the cyano C sites. In a related study, keeping track not only of the magnitude but also the orientation of the principal components of 13C shielding in an alkene and an alkyne proves to be important in analyzing Z2–bonding to transition metals.113 If one examines only the values of the shielding components of 13C in the acetylene sites of (Z2–diphenylacetylene)Pt(PPh3)2, a quick conclusion can be easily drawn indicating that the least and most shielded components decrease by 60 ppm, while the intermediate component s22 changes only slightly. However, by keeping track of the orientation of the shielding tensor in free diphenylacetylene (DPA) and how this changes with the formation of the complex, it becomes evident that the changes in the acetylene 13C shielding principal components upon Z2-coordination to Pt are less than straightforward. There are dramatic changes in the orientation of the tensor. In free DPA, the most shielded component, s33, lies along the triple bond, and upon coordination to Pt, this component decreases by about 200 ppm, making it the new intermediate component, s22, in (Z2-DPA)Pt(PPh3)2. The intermediate component, s22, in DPA lies perpendicular to the triple bond, along the same plane deﬁned by the aromatic rings. Upon coordination, the shielding in this direction increases by about 130 ppm, rendering this component the most shielded (s33) in (Z2-DPA)Pt(PPh3)2. The least shielded component, s11, bears the same orientation (normal to the plane deﬁned by the atoms in DPA) in free and coordinated DPA, except that upon complexation this component becomes further deshielded by about 70 ppm. These changes are markedly diﬀerent from the ones observed for 13C shielding in an alkenyl ligand, as exempliﬁed by (Z2-trans-stilbene)Pt(PPh3)2. In stilbene, in contrast to acetylene, coordination leads to a shielding increase in all directions, thereby conserving the Nucl. Magn. Reson., 2007, 36, 50–71 | 59 This journal is

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orientation of the tensor. Exploring the relationship between electronic structure and the principal components of the 13C shielding tensor in aromatic quinolines, Casabianca and de Dios114 have found an interesting correlation between the magnitude of the least shielded component of these tensors, s11, in 7-subsituted quinolines and their binding strength to heme. In examining the orientation of the principal axis system of 31P shielding in Pt(II)-phosphine complexes, it has been suggested that the tensor orientation is more likely to follow a pseudo plane deﬁned by the P atom and the two other atoms attached to it rather than the directions of the bonds to the P atom.115 The 15N and 31P shielding tensors have been reported for the adduct between silver nitrate and triphenyl phosphine.116 Due to a relatively large quadrupolar coupling in asymmetric environments and low sensitivity, 39K solid state NMR spectroscopy is challenging. With the use of a quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) method developed by Larsen et al.,117,118 Widdiﬁeld and Schurko119 have measured the solid state 39K NMR parameters in the polymeric cyclopentadienyl complex of potassium. The contribution of chemical shift anisotropy to the powder pattern of 39K NMR spectrum of polymeric potassium metallocenes is found to be insigniﬁcant. Theoretical calculations indicate a possible range of 9–63 ppm (170–1200 Hz in a 9.4 Tesla magnet) for the shielding tensor span, relatively small compared to the observed quadrupolar coupling constant of 2.6 MHz. Half-sandwich cyclopentadienyl complexes of niobium(I) and niobium(V) have been the subject of recent solid state 93Nb and 13 C NMR studies.120 The change in oxidation state of Nb from I to V leads to an appreciable increase (about 50 times) in the quadrupole coupling constant. The span of the 93Nb shielding tensor in CpNb(CO)4 is found experimentally to be 35 ppm, while B3LYP/6-311G**(16s10p7d on Nb) calculations predict a much larger value, 479 ppm. Similarly, calculations likewise overestimate the shielding tensor span in CpNbCl4, 468 ppm, to be compared with 150 ppm from experiment. In both cases, theory underestimates s11 and overestimates s33, leading to a much higher tensor span. Various lanthanum(III) coordination compounds have been examined by solid state 139La NMR spectroscopy and relativistic DFT calculations.121 In this set of compounds, the range of 139La quadrupolar coupling constants is found to be within 10–36 MHz, and the span of the 139La shielding tensor encompasses 50–260 ppm (3500–18600 Hz in an 11 Tesla magnet). The range of isotropic 139La NMR chemical shifts is about 250 ppm. In order to extract this information, accurate simulation of spectra obtained at two diﬀerent ﬁelds, 11.75 and 17.60 Tesla) is critical. The shielding anisotropy contribution to the line shape is obviously smaller than that of the quadrupolar coupling, thus, requiring a second higher magnetic ﬁeld measurement. An interesting trend seen in this set of lanthanum compounds is the observed correlation between the isotropic 139La NMR chemical shift and the coordination number around La. As the coordination number around Lanthanum increases, so does the shielding. Comparison between ZORA-DFT calculated shieldings and experimental 139La NMR chemical shifts yields a slope of 0.89 with an R2 of 0.89, indicating modest agreement between theory and experiment. A slope smaller than 1.0 was also found for 183W calculations (0.75) in another study.60,61 Similar to the 93Nb study, the 139La shielding tensor spans appear to be overestimated in the calculations. Using multiple magnetic ﬁelds (7.0, 9.4, 11.7, 14.1 and 17.6 Tesla), 139La shielding tensors have been measured for anhydrous lanthanum(III) halides.122 Referenced to a 1.0M LaCl3 (aq), the measured isotropic shifts in the anhydrous halides are: 135 ppm (LaF3), 305 ppm (LaCl3), 400 ppm (LaBr3), and 700 ppm (LaI3). The spans are likewise increasing with increasingly heavier halogen: 35 ppm (LaF3), 50 ppm (LaCl3), 100 ppm (LaBr3), and 650 ppm (LaI3). ZORA-DFT calculations agree qualitatively with these measured tensors. Titanium NMR presents a bigger challenge as two isotopes, 47Ti and 49Ti, both quadrupolar, share almost identical frequencies (45.102 and 45.112 MHz, respectively) even at 18.8 Tesla. By taking advantage of the diﬀerence in spin quantum number (I ¼ 5/2 for 47Ti and I ¼ 7/2 for 49Ti), pulse sequences can be employed to select a given 60 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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isotope.123 Applying this new experimental procedure, a small anisotropy (about 30 ppm) has been observed for the 49Ti shielding in the rutile form of titanium dioxide. The sensitivity of both shielding and quadrupolar coupling to symmetry enables the use of these NMR parameters in probing the geometries of transition metal complexes. In a solid state 95Mo NMR study by Forgeron and Wasylishen,124 dodecahedral (D2d) and square antiprismatic (D4d) geometries can be distinguished by examining both shielding and electric ﬁeld gradient tensors. K4Mo(CN)8 2H2O, which exhibits approximate dodecahedral symmetry, provides a 95Mo shielding tensor span of about 1160 ppm. On the other hand, Tl4Mo(CN)8, which crystallizes in a square antiprismatic form, exhibits a span of about 1350 ppm. Lastly, a recent review and compilation of solid state NMR data of quadrupolar halogens; 35/37Cl, 79,81 Br and 127I, has been written by Bryce and Sward.125 2.2 Shielding surfaces and rovibrational averaging Huda´ky and Perczel have recently added histidine to the list of amino acid residues, whose 13C shielding surfaces have been theoretically constructed as a function of protein dihedral angles.126 In this latest work, a closer inspection of backbone 1H and 13C chemical shifts reveals the possibility of extracting additional detailed structural information, such as the position of the histidine residue in a helix or sheet region of a protein. It appears that the chemical shifts of residues near the ends of these secondary structures exhibit greater variation from the values predicted by the dihedral angles alone. The dependence of 13C chemical shifts on conformation has been examined in two aryltetralin lignan lactones, polygamain and morelensin.127 These two lactones diﬀer from each other in terms of conformational rigidity, polygamain being the more rigid of the two. Morelensin owes its ﬂexibility to the two methoxy groups (ortho to each other) bound to the aromatic ring. In polygamain, a ﬁve-membered di-ether ring replaces the two methoxy groups, which leads to a restricted geometry. A conformational search for both lactones yields 4 energy minima for polygamain and 12 for morelensin. Calculated chemical shifts weighted by a Boltzmann distribution over these minimum structures are shown to compare favorably with experiment. Proposed structures for the cucurbit[6]uril-sperminecomplex have been validated by 1H shielding calculations.128 Calculating NMR chemical shifts on structures suggested by conformational searches have been applied to elucidate the structure of the natural products jungianol and mutisianthol.129 Likewise, 13C NMR shielding calculations have found application in the conformational study of liquid crystalline polymers that contain an ester functional group in its mesogenic unit.130 In this work, the shielding of the carbonyl C is predicted to be aﬀected by its conjugation with the phenyl ring ester and by the dihedral angle of the ring–ring linkage. A similar conformational analysis in combination with calculations of chemical shifts has been performed on N-substituted derivatives of piperidine and pyrrolidine.131 The conformers that lead to a better agreement between calculated and observed NMR chemical shifts reveal speciﬁc weak hydrogen bonding of the type C–H O. Another set of compounds in which 13C and 1H chemical shifts have been explored as a function of dihedral angles are the calix[n]arenes.132 The two dihedral angles in these systems deﬁne the conformation around the CH2 group that joins the two phenyl rings. These dihedral angles determine whether the two aromatic rings are syn- or anti- with respect to each other. Using a model structure that involves two p-methoxytoluene groups connected at C-3 by a single methylene, the two dihedral angles were systematically varied by 301 and chemical shifts were calculated at each conformation, producing a shielding surface of the two dihedral angles. With this surface, it is now possible to explain the chemical shifts observed for larger calixarenes that exhibit unusual orientation of two adjacent aromatic rings. An interesting 1H shielding surface has been calculated for the reaction coordinate that involves a proton transfer from His57 to Asp102 in serine protease trypsin.133 This shielding surface shows Nucl. Magn. Reson., 2007, 36, 50–71 | 61 This journal is

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maximum deshielding for the 1H nucleus when the proton is near the midway point between the two residues. These results are similar to the 1H shielding surfaces constructed for the proton-exchange pathway in porphyrin and porphycene.134 In addition to 1H shielding, 15N shielding surfaces are likewise calculated for porphyrin and porphycene, but in contrast to 1H, the 15N shielding is monotonic, with the N losing the proton becoming deshielded, while the N gaining the proton becoming shielded with the proton transfer. 2.3 Isotope shifts Secondary isotope eﬀects on NMR chemical shifts are due to slight diﬀerences in the rovibrationally averaged geometry. These eﬀects on shielding generally diminish as one goes farther from the site of isotopic substitution. Hence, in the Schiﬀ bases of gossypol the signiﬁcant deuterium-induced isotope eﬀects observed for the 13C shielding (about 0.34 ppm) of the carbon directly attached to an N atom indicate that these Schiﬀ bases of gossipol are mostly enamines, the form that contains an exchangeable proton on the nitrogen.135 Similarly, from deuterium-induced isotope shifts, it is likewise suggested that the proton transferred N–H form is the dominant species in lithium salts of amino acid-derivatized Schiﬀ bases.136 Long-range deuterium isotope eﬀects (in the range 0.036 to 0.106 ppm) on a 13C site that resides ﬁve single bonds away from the site of deuteration have been observed for a series of thioanilides.137 In these compounds, the hydrogen replaced by deuterium is participating in an intramolecular hydrogen bond. Deuterium isotope eﬀects in systems involving intramolecular hydrogen bonds have found application in characterizing b-diketones.138 It is a common assumption that diﬀerences in observed secondary isotope eﬀects on two carbonyl carbons at various temperatures can be used to assess if one is dealing with a single-well or a double-well potential surface for the intramolecular hydrogen bond in these systems. As yet, this has not been rigorously demonstrated. Three factors have been suggested as responsible for the variations observed in deuterium isotope eﬀects on 13C NMR chemical shifts in o-hydroxy Schiﬀ bases,139 namely the nature of the substituents on the aromatic ring, the substituent on the enamine carbon, and whether the nitrogen atom is bound to an aromatic or aliphatic group. Finally, recent 1H, 13C and 19F NMR measurements on CHF3 in the gas phase have yielded the following secondary isotope eﬀects: 1 19 D F(13/12C) ¼ 0.126 ppm and 2D19F(2/1H) ¼ 0.812 ppm.140 These values are in the limit of zero density at 300 K. 2.4 Intermolecular eﬀects on nuclear shielding A recent review on the eﬀects of non-covalent interactions on NMR parameters has been made available.141 Included in this review is a survey of quantum chemical methods as well as supermolecule and molecular dynamics approaches for calculating solvent eﬀects on nuclear shielding. Oldﬁeld142 presents a review on electrostatic eﬀects on NMR parameters and discusses how recent developments in the ﬁeld can be used to explore various aspects of protein structures and electrostatic properties. For intermolecular eﬀects on NMR shielding, 129Xe NMR spectroscopy continues to be an area of active research. Vukovic et al.143 have performed the ﬁrst calculation of the intermolecular shielding of a Xe atom in the presence of a paramagnetic species, an O2 molecule. In contrast to diamagnetic linear molecules such as CO and N2, interaction with O2 leads to extrema at y ¼ 451 and 1351 (where y is the angle that Xe, the center of mass of O2 and one of the O atoms make). The explanation provided for this behavior is drawn from the fact that the spin density comes mainly from the antibonding p orbital of O2, which consists of a nodal plane passing through the center of the O2 molecule. Therefore, the greatest interaction between Xe and the spin density of O2 occurs at the orientations, y ¼ 451 and 1351. With 62 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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diamagnetic systems, 129Xe maintains its role as an important probe in characterizing porous materials. Shape-persistent macrocyles are among the porous materials that can be studied with 129Xe nuclei as probes, and with hyperpolarized 129Xe, a quick and sensitive characterization of the porosity in these materials has become possible.144 Ooms et al.,145 for example, have used 129Xe NMR spectroscopy in investigating potentially porous organic macrocyclic materials. The speciﬁc systems examined in this recent study consist of ordered solid materials derived from conjugated pyridine-containing macrocycles. Several resonances are observed for Xe in these materials. A broad peak near 190 ppm (referenced from the gas peak of 7 Torr of Xe in 7 Torr of N2 and 686 Torr of He) is assigned to Xe atoms occupying sites near the end of the channel, thereby interacting more with phenyl groups of the macrocycle. This interaction is supposed to lead to greater deshielding of the 129Xe nucleus. A peak observed near 130 ppm is assigned to Xe atoms inside the cavity site, which is less conﬁned compared to the end of the channels. Changing the pyridine into a phenyl group in these macrocycles leads to a greater deshielding of the peak near 130 ppm. This diﬀerence is explained by a comparison between ab initio calculations performed on a Xe atom interacting with benzene and with pyridine. The diﬀerences in chemical shifts observed are in the same direction as those predicted by the model calculations, in which a C–H (in benzene) causes greater deshielding of Xe than an N (in pyridine) atom does. However, calculations of Xe shieldings at particular locations next to the model fragment cannot be used to compare with experiments; averaging over all Xe positions in a grand canonical scheme is necessary. Sears et al.146 have extended the use of hyperpolarized 129Xe NMR spectroscopy to monitoring the formation of microporous AlPO4-5 and AlPO4-18. By following the changes in the 129Xe NMR chemical shifts, one is able to see that beginning with an amorphous phase, AlPO4-5 is ﬁrst formed, which is then converted to AlPO4-18. 129Xe inside AlPO4-5 has a chemical shift of 63 ppm (referenced to Xe gas at zero density), while those inside AlPO4-18 have a chemical shift of 74 ppm. A combination of grand canonical Monte Carlo (GCMC) simulations and 129Xe shielding surfaces has also been successfully applied to Xe atoms adsorbed in nanochannels of ionic crystals of ()-[Co(en)3]Cl3.147 In this particular case, the calculated span for an axially symmetric 129Xe shielding tensor is 105 ppm, in close agreement to the observed value of 100 ppm. In this example, Xe in the channels did not exhibit the expected changes in line shape with increasing Xe occupancy. GCMC simulations revealed that Xe–Xe contributions are minimal in these channels since Xe singly occupy cell-like pores rather than uniform-diameter channels.147 Telkki et al. in a series of studies148–150 have illustrated the use of variable temperature 129Xe NMR spectroscopy in determining and characterizing pore sizes and volumes in controlled pore glasses. Work on optimizing Xe biosensors for detecting protein interactions continues.151 The new biosensors consist of a Xe-binding cryptophane-A cage, a short peptide to make the sensor water-soluble, and a moiety that speciﬁcally binds to a target protein molecule. In this study, a biotinylated sensor is used and the target protein is avidin. The spacing between biotin and the crytophane-A cage can be controlled by a linker, whose length plays a signiﬁcant role in the line width of the observed 129Xe resonance. Furthermore, the dependence of the Xe chemical shift upon binding on the linker length is totally consistent with the sensing mechanism via mechanical cage deformation proposed earlier.152 The study shows that a ﬂexible linker of moderate length (about 12–30 bonds) leads to reasonably narrow lines in the 129Xe spectrum, thus, increasing its signal-to-noise ratio and sensitivity. Hilty et al.153 have demonstrated that such biotinylated Xe biosensors could also be used for magnetic resonance imaging. Lastly, due to the sensitivity of 129Xe NMR chemical shifts to the environment, an NMR thermometer based on 129Xe NMR spectroscopy has been proposed.154 Gas phase NMR measurements enable the extrapolation of measured resonances to zero density, thereby providing the chemical shifts for an isolated molecule. In Nucl. Magn. Reson., 2007, 36, 50–71 | 63 This journal is

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addition to speciﬁc studies on the molecule sevoﬂurane ((2,2,2-triﬂuoro-1-(triﬂuoromethyl) ethyl ether)155 and benzene,156 Jackowski157 has recently compiled NMR chemical shifts for a variety of gas phase molecules, extrapolated to the isolated molecule limit. This recent work also includes the gas phase density dependence of the NMR parameters. Since hydrogen bonding plays an important role in a wide array of systems, the study of its eﬀects on NMR chemical shifts remains a vigorous area of research. For instance, one can take advantage of the eﬀects of hydrogen bonding on chemical shifts to discriminate between water molecules in hydrophilic and hydrophobic environments in bone tissue.158 By closely deciphering the observed 1H and 13C chemical shifts in anomeric maltose, Yates et al.159 have found a quantitative correlation between the NMR chemical shifts and the geometry (distance and angle) of weak CH O hydrogen bonds. In a recent work on crystalline uracil, Ida et al.160 have determined that 17O NMR shielding tensors are more diﬃcult to reproduce theoretically when the O site is involved in weak CH O hydrogen bonding as opposed to the stronger NH O arrangement. A similar situation is apparent with the electric ﬁeld gradient tensors. This diﬃculty is attributed to the uncertainty in the hydrogen atom positions and it appears that partial geometry optimizations of cluster models derived from X-ray structures are necessary. This part of the computational protocol has been in use for some time in many other hydrogenbonded systems, as reported in this series of volumes. A comparison between CH O and NH O hydrogen bonds and their eﬀects on 1H NMR chemical shifts in monohydrated 2,4-dithiothymine has been reported by He et al.161 Focusing on typical hydrogen bonds, OH O, Wong et al.162 have used 17O NMR spectroscopy to characterize hydrogen bonds in carboxylic solids. Their ﬁndings indicate that the 17 O nucleus in O–H becomes deshielded with shorter hydrogen bond distances while that of CQO becomes shielded. Balandina et al.163 have used model hydrogenbonded dimer structures to reproduce the observed 1H, 13C and 15N NMR chemical shifts in functionalized derivatives of quinoxalines. 1H and 13C NMR chemical shifts, as expected, are also useful in determining which tautomeric form is dominant in N-substituted acridin-9-amines.164 13C NMR shielding tensors have been utilized to characterize the hydrogen bonded structures of amino acids that have been crystallized in the presence of inorganic acids.165 This recent work suggests that the observed and calculated 13C shielding principal components (mainly the diﬀerence between s11 and s22) could be used to distinguish between four diﬀerent types of interactions possible for amino acid—inorganic acid complexes. These four categories are: (1) the amino acid is formally a carboxylate, COO H–X, (2) the proton is localized at the carboxylate, COOH X, (3) the proton resides at the central region, and (4) there is a low barrier hydrogen bond with disordered proton positions. Similar work has been done on 2-amino-pyridine betaine166 and 3-(2amino-pyridinium)-proprionate monohydrate.167 Kolehmainen et al.168 have incorporated explicit acetone molecules in their calculation of 13C chemical shifts in polychlorinated biphenyl (PCB)-derived carboxylic acids. This model provides one acetone molecule as a hydrogen bonding partner for each proton in the PCB-derived carboxylic acid molecule. It has been known for some time that a cluster that includes all surrounding hydrogen bond partners are necessary to provide calculated NMR chemical shifts that agree with experiment. A recent example is the calculation of 13C chemical shifts observed for the imidazole carbon sites in various histidinecontaining dipeptides.169 Instead of using molecular clusters to calculate shielding tensors in solids and extended networks, one could use the method devised by F. Mauri et al.170 To reproduce the 13C, 14N, 15N, and 17O shielding tensors in amino acids, Gervais et al.,171 have employed the plane-wave pseudopotential approach in the solid state. The results are satisfactory even for the sites that participate in hydrogen bonding. The number of hydrogen bonds is particularly important in interpreting the quadrupolar coupling constants as well as the shielding tensors for Cl ions172 in various amino acid—HCl salts. 31P NMR chemical shift tensors have 64 | Nucl. Magn. Reson., 2007, 36, 50–71 This journal is

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been measured and calculated for hypervalent oxyphosphoranes and polymeric orthophosphates.173 Based on the computational portion of this work, solvents eﬀects on 31P shieldings in pentaoxyphosphoranes are found to be very small (o0.5 ppm). Proton NMR shielding computations have been performed on the hydrogen molecule to see if its chemical shift would be able to distinguish between small and large cages in structure II clathrates.174 The results suggest that the diﬀerence is in the order of 0.1 to 0.2 ppm. Alkali metal-reduced mesoporous titanium oxides have been examined by solid state 23Na and 7Li NMR spectroscopy.175 The chemical shifts and line widths of the observed resonances provide information regarding the reduction level of these materials. Other alkali nuclei (39K and 87Rb) have been used to characterize Gquadruplex structures.176,177 The eﬀects of Mg21 coordination to the NMR shielding tensors of nuclei in nucleotides have been calculated.178,179 195Pt NMR shielding calculations are found to be challenging not only because of the large basis set, relativistic and electron correlation requirements, but also solvent eﬀects.180 As in other nuclei, the solvent can aﬀect the chemical shift via two ways, perturbing the electronic structure of the solute and/or altering its geometry. A lighter nucleus, 59 Co, poses similar challenges. The electronic structure of the transition metal complex depends on the metal ligand distance (which changes with temperature). This has been known from the early days of crystal ﬁeld and ligand ﬁeld theory. Neither this nor the abovementioned 195Pt study includes these vibrational-electronic eﬀects. Rovibrational corrections bring calculated 59Co shieldings closer to experiment but not when the data were obtained in aqueous solution.181 In these calculations the mean absolute deviations between theory and experiment is in the order of 500–760 ppm, to be compared with the observed chemical shifts range of almost 20 000 ppm. 93Nb NMR spectra of a series of inorganic niobates have been reported.182 In this set of niobates, the isotropic 93Nb NMR chemical shift oﬀers clues with regard to the coordination number around Nb. An accompanying increase in 93Nb shielding is observed with increasing number of O atoms bound to Nb. Ring-current eﬀects in porphyrins have been explored by several studies during this reporting period. First, Steiner et al.183 have demonstrated through an ipsocentric-orbital based model that the central charge in metalloporphyrins changes the pathway of global p currents. Starting with a neutral cation (Z ¼ 0), the global p current takes an inner pathway, and as the charge at the center becomes more positive (Z ¼ 2), the current becomes bifurcated, and with Z ¼ 4, the current already takes an outer path. The same model has been applied to visualize the ring currents in an extended porphyrin, amethyrin.184 In this expanded porphyrin, the internal NH protons are deshielded while the bridge CH protons are shielded, suggesting the presence of a global paratropic ring current. The recent work shows that indeed there is a dominant paratropic current concentrated on the inner 20-site cycle, but there is also a weaker diatropic circulation on the outer 24-site pathway plus a combination of local 5-site diatropic current on the six pyrollic rings. By fusing 10 pentagons around a central decagon, as in [5,10]-coronene (C30H10), it has been demonstrated via an ipsocentric ab initio mapping of currents that this molecule can support diatropic currents on the inner part (hub) and paratropic currents on the outer pathway (rim).185 Calculated magnetic ﬁeld-induced current densities have also been used to verify the aromaticity or anti-aromaticity in heteropentalenes formed by two phosphole units,186 and in fullerenes and other curved carbon networks.187 Soncini et al.188 have veriﬁed the independence in choice of gauge origin of the continuous transformation of the origin of the current density (CTOCD) method. The paramagnetic zero (PZ2) variant of CTOCD has been used to characterize the magnetic and electronic properties of dicyclopenta-fused pyrene congeners.189 Sebastiani 190 has developed a current density calculation based on a pseudo-potential plane-wave approach. This method is then applied to current density and NICS calculations in the solid state. Examples of systems in which a Nucl. Magn. Reson., 2007, 36, 50–71 | 65 This journal is

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successful plane-wave current density calculation has been implemented are calixhydroquinone, graphite and various types of carbon nanotubes. The gauge-including projector augmented-wave (GIPAW) approach has also been used successfully to explain the observed 13C solid state NMR spectra of carbon nanotubes.191 Static and magic-angle spinning 13C NMR spectra have been measured for carbon nanohorn aggregates.192 Two distinct resonances are observed. The ﬁrst one, with an isotropic shift of 124 ppm, has a short longitudinal relaxation time, and is assigned to the nanotubelike horns on the surface of the particles. The second peak is around 116 ppm and exhibits a longer relaxation time, and is assigned to the graphite-like regions of the aggregate. Visualizing ring currents is more reliable than the use of isotropic NMR chemical shifts in gauging whether a system is aromatic or anti-aromatic. In the absence of induced ring current pictures, as Faglioni et al.193 have demonstrated on unsaturated polycyclic compounds, the out-of-plane component of the shielding tensor is a more reliable measure of aromaticity, compared to nucleus-independent chemical shifts (NICS). NICS being average isotropic quantities, provide less complete information about the eﬀects of ring currents compared to current density maps. Still, NICS do oﬀer a qualitative indication of the presence of ring currents. For example, four porphyrin groups have been made to fuse, forming a planar cyclooctatetraene core.194 This compound, as characterized by NICS calculations, is shown to exhibit strong paratropic shifts around the cyclooctatetraene core and weak diatropic shifts inside each of the porphyrin cores. NICS are likewise useful for predicting intermolecular eﬀects on NMR chemical shifts that arise from nearby aromatic rings. Facelli195 has constructed a three dimensional grid above the molecular plane of systems like benzene, naphthalene and coronene. The NICS evaluated at these grid points are then ﬁtted to a dipolar type function ((1–3 cos2y)/r3). The computation of NICS has also been utilized in characterizing dimer structures of quinolinebased antimalarial drugs.196 Murata et al.197 have managed to encapsulate a hydrogen molecule inside the fullerene C60. The synthesis involves a 4-step closure of a 13-membered ring opening. The 1H NMR chemical shift of the encapsulated hydrogen molecule is measured for each of the intermediates. A gradual downﬁeld shift is observed as the fullerene cage is closed. The calculated NICS agree qualitatively with this experimental trend. In the case of N-phenyl amino-substituted thio(seleno) acrylamides, in addition to the ring current eﬀects from the phenyl substituent, the anisotropic eﬀects of either CQS or CQSe are equally important in diﬀerentiating conformers.198 Lastly, 1H nuclear magnetic shielding tensors have been carefully measured for the biphenyl molecule.199 In this recent work, assignment is obtained by utilizing semiempirical and quantum chemical calculations of intermolecular shielding contributions. These contributions are then subtracted from the measured tensors to extract the shielding components for the isolated molecule. The correctness of the calculations is gauged by evaluating how well the resulting tensors obey the molecular symmetry relations. Expressed in icosahedral tensor representation, the error is found to be under 0.5 ppm. It has been suggested that more accurate values of nuclear magnetic dipole moments may be obtained from measurements of resonance frequencies in the same sample containing a very dilute gas consisting of molecules having two or more NMR-active nuclei. The frequencies can be extrapolated to zero density to eliminate intermolecular eﬀects. The ratios of experimental frequencies and accurate calculations of the isotropic shielding for the two nuclei permit the ratio of magnetic dipole moments to be checked for accuracy.200

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Applications of nuclear shielding Shigeki Kuroki,a Naoki Asakawab and Hidekazu Yasunagac DOI: 10.1039/b601639c

1. Introduction The report covers and introduces studies on the application of nuclear shielding and related NMR chemical shifts, which were made in the world from 1 June 2005 to 31 May 2006. The shieldings of particular nuclear species are described in the following section according to their position in the periodic table. Although there is a great number of articles on NMR spectroscopy during the period of this review, the coverage of this chapter is restricted to widely available and common journals, which are published in English as a general rule, due to space limitation. The report also introduces a couple of topics, which should have been mentioned in the volume 35 of this book.

2. Shielding of particular nuclear species The NMR experiments for most elements contained in molecules were made in the course of physical, chemical or biological studies during the period covered by the report. The simple chemical structure determination and related studies of synthesised and natural products are excluded in the report, and the review articles are given as necessity requires. 2.1 Group 1 (1H, 2H, 3H,

6,7

Li,

23

Na,

39

K,

87

Rb,

133

Cs)

2.1.1 Hydrogen (1H) (I =1/2). The proton shielding tensors for a spherical crystal of biphenyl compound were determined by using line-narrowing multiple pulse techniques.1 The assignment of the measured tensors to the corresponding proton sites was given and intermolecular shielding contributions were calculated. The isolated-molecular shielding tensors obtained from experiments and calculated intermolecular contributions were compared with isolated-molecular quantum chemical results. It was found that the least shielded direction of all protons is the perpendicular to the molecular plane for the compound. Solution-state 1H and 13C NMR spectroscopy and density functional theory quantum mechanic conformational modeling were combined with solid-state cross-polarization/magic angle spinning (CP/MAS) 13C NMR spectroscopy for the research of cis-cyclooctene and cis-cyclononene medium ring stereochemistry.2 The theoretical possibility of stereochemically labeled chiral medium rings having diastereomeric conformational subtypes was shown to exist in practice for some of the 2,5-benzoxazocine and 2,6benzoxazonine skeletons. The structure of 3-hydroxy-3-methyl-pyrido [2,1-c][1,4]dihydrooxazinium chloride and 3-hydroxy-3-phenyl-pyrido[2,1-c][1,4] dihydrooxazinium bromide was determined by using 1H and 13C NMR spectroscopy.3,4 Correlations between the experimental 1H and 13C NMR chemical shifts and the GIAO/B3LYP/6-31G(d, p) calculated magnetic isotropic shielding tensors were a

Tokyo Institute of Technology, Department of Chemistry and Materials Science, 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8552, Japan. E-mail: [email protected]; Tel: +81-3-5734-2880 b Tokyo Institute of Technology, Department of Biomolecular Engineering, Graduate School of Bioscience and Biotechnology, 4259 Nagatsuda, Midori-ku, Yokohama, Kanagawa, 226-8501, Japan. E-mail: [email protected]; Tel: +81-45-924-5796 c Kyoto Institute of Technology, Department of Chemistry & Materials Technology, Kyoto Sakyo-ku Matugasaki Gosyokaido-tyo, 606-8585, Japan. E-mail: [email protected]; Tel: +81-75-724-7562

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reported. A good linear relationship between the experimental and calculated data for carbons was obtained. The interaction between Rh or Pt and H–C or H–N was investigated.5 There are large downﬁeld 1H NMR chemical shift changes on metal bonding, accompanied by changes in shielding tensor orientations. The NMR signal assignments for (di-)cyclopenta-fused pyrene congeners, cyclopenta[cd]-, dicyclopenta[cd, fg]-, dicyclopenta[cd, jk]- and dicyclopenta[cd, mn]pyrene were achieved using two-dimensional (2D) NMR spectroscopy.6 Substituent-induced chemical shifts in the pyrene core induced by annelation of cyclopenta moieties were discussed and eﬀects of dicyclopenta topology on electronic structure were illustrated. The comparative study of the calculated ab initio 17O and 1H shielding constants for hypothetical water clusters (H2O) n (n = 2 – 6, 12 and 17) was reported.The densityfunctional theory (DFT)(B3LYP)/aug-cc-pCVDZ calculations of shielding constants were performed for all clusters and the correlation of the changes in the 1H shielding constants on intra- and intermolecular distances was observed.7 The NMR-shielding of cucurbit[5]uril, decamethylcucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril and cucurbit[8]uril were studied by DFT calculations.8 All the molecules were found to be highly symmetric with a distinct geometric ﬂexibility and their chemical complex building ability was discussed. The authors also reported the NMR-shielding of cucurbit[6]uril-spermine host-ligand complexes investigated by DFT calculations and measurements.9 Cucurbit[6]uril and spermine can form complexes with two diﬀerent minimum energy geometries having a perfect inversion symmetry and they show corresponding characteristic diﬀerences in NMR shielding. The conformational properties of the aldol adducts of some N4-isopropyl-oxadiazinones were studied by 1H NMR spectroscopy and the shielding aspect observed clearly suggested the presence of the anti-parallel arrangement.10 It was found that solution state conformation of the N4-Me and N4-isopropyl-oxadiazinones involves anti-parallel carbonyls in contrast to the solid state evidence of the X-ray crystallographic data of oxadiazinone. Three Rh phosphinite complexes with the general structural formula [RhCl(i-Pr2POXy)(L)]2 (Xy = 2, 3-xylyl; L = PPh3, PMe3, t-BuNC) were synthesised and characterised.11 The 1H NMR chemical shielding calculations on a geometry-optimized model complex were used for assignments. The eﬀectiveness of a calix[4]resorcarene prepared from N-methyl-L-alanine as a chiral NMR discriminating agent was studied comparing to the L-prolinylmethyl derivative.12 Aromatic resonances of the substrates show substantial upﬁeld shifts because of shielding from the aromatic rings of the calix[4]resorcarene. The several resonances in the 1H NMR spectra exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends on interactions of the substituent groups of the substrates with the prolinylmethyl groups of the calix[4]resorcarene. The NMR spectra of the Diels-Alder adducts from 3,6-dibromophencyclone reacted with Nethylmaleimide, N-n-propylmaleimide and N-n-butylmaleimide were studied by 1H and 13C NMR and rigorous assignments for protonated carbons were obtained with the heteronuclear chemical shift correlation spectra (HETCOR).13 Endo Diels-Alder adduct stereochemistry was supported by substantial magnetic anisotropic shielding eﬀects in the 1H NMR spectra of the alkyl groups. Alkyl proton NMR shielding magnitudes in the adducts were evaluated and the relation between the adduct geometries and the observed shielding magnitudes was derived by using ab initio Hartree-Fock level calculations. The adducts obtained from phencyclone and Nalkylmaleimides were studied by 1H and 13C NMR and substantial magnetic anisotropic shielding eﬀects in the 1H spectra of the N-alkyl groups of the adducts were revealed.14 Magnetic anisotropic shielding magnitudes for alkyl group protons in the adducts were calculated relative to corresponding proton chemical shifts in the maleimides. The existence of diﬀerent contributing conformers for the adducts was discussed with respect to implications regarding experimental observed anisotropic shielding magnitudes and their calculated energies. The charges on methyl-4acetoxybenzothiophene-6-carboxylate and 4-hydroxybenzothiophene-6-carboxylic acid were calculated by the parametric quantum mechanic molecular model AM1 Nucl. Magn. Reson., 2007, 36, 72–112 | 73 This journal is

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and PM3 and were correlated with 1H NMR chemical shifts.15 Thermodynamic functions (heats of formation, enthalpy and entropy) of these molecules were calculated in the temperature range 100–1000 K. It was shown that the diﬀerence in the 1H NMR chemical shift of a protic hydrogen in DMSO and CDCl3 solvents is directly related to the overall hydrogen bond acidity for a wide range of solutes.16 The NMR method allows the determination of the Abraham solute hydrogen bond acidity parameter for individual protic hydrogens in multifunctional solutes. The behaviour of water at mosaic hydrophilic/hydrophobic surfaces of diﬀerent silicas and in biosystems was studied in diﬀerent dispersion media over wide temperature range using 1H NMR spectroscopy.17 It was found that there are weakly associated interfacial water (1H NMR chemical shift delta(H) = 1.1–1.7 ppm), strongly associated interfacial water (delta(H) = 4–5 ppm) and continuous interfacial layer. Hydrogen-bonding eﬀects in the real crystalline structure of 9-methyladenine were studied using calculated electric ﬁeld gradient (EFG) and chemical shielding (CS) tensors for 1H, 2H, 14N and 15N via density functional theory.18 The chemical shielding anisotropy (Ds) and chemical shielding isotropy (s iso) were also reported for 1H and 15N. The results indicated that N(10) (imino nitrogen) has a major role in H-bonding interactions, whereas that of N(9) is negligible. 1H NMR shielding constants and chemical shifts for hydrogen guests in the cages of structure II clathrates were calculated using density functional theory and the gauge-invariant atomic-orbital method.19 The calculated chemical shifts of single hydrogen molecules in the small and large structure II cages are 4.94 and 4.84 ppm, respectively. Multiple occupancy of the guests in the cage changes the chemical shift of the guests by approximately 0.2 ppm. Porphyrin and porphycene was studied using DFT for both the spin–spin coupling constants and the shielding constants paying attention to their changes during the process of proton exchange.20 The calculated nuclear spin–spin coupling constants and shielding constants were analyzed as functions of the progress of the proton transfer between two nitrogen atoms. The isotropic shielding constant shows a strong deshielding of the nitrogen nuclei when the proton migrates away by the exchanging. It can be said that both the isotropic shielding of the exchanged protons and the shielding anisotropy exhibit a minimum close to the transition states. The presence of intermolecular hydrogen bonds between the adducts of formula [N(CH2CH2)3N]–H–[OOC(CH2)nCOOH] (n = 1–7) was studied by 1H MAS and 15 N CP/MAS spectroscopy.21 Correlations among isotropic 1H and 15N chemical shift data and the N–O distances of the atoms involved in the hydrogen bond interaction were found for the adducts. Density functional theory was applied to explore changes upon hydrogen bonding in the 1H and 15N shielding parameters and it was also found that the calculated values agree with the experimental value. Hydrogen/deuterium isotope eﬀects on the 15N NMR chemical shifts were also investigated. 2.1.2 Deuterium (2H) (I = 1). The 2H–15N and 2H–1H NMR chemical-shift correlations and distance measurements were made for cytosine monohydrate, whose acidic protons can readily be replaced by deuterons by recrystallisation from D2O.22 The 2H NMR spectroscopy provides information complementary to 1H NMR data and can be performed in full analogy to 1H spectroscopy in solid-state NMR, when the NMR experiments are conducted in a ‘‘rotor-synchronized’’ fashion under fast MAS. 2H and 13C MAS correlation experiments were made for a uniformly 2H, 13C and 15N labeled Nac-Val and 2H and 15N labeled dipeptide NacVal-Leu-OH.23 The experiments involve the measurement of the 2H tensor parameters by evolution of the 2H chemical shift. A novel two-dimensional 2H NMR technique was introduced for determination of both quadrupole and chemical/ paramagnetic shift tensors and their relative orientation.24 The properties of the novel technique were demonstrated using computer simulation. The technique was 74 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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applied to benzoic acid-d1 (C6H5CO2D) and copper(II) chloride dihydrate-d4 (CuCl2 2D2O). Hydrogen-bonding eﬀects in the real crystalline structure of 9methyladenine were studied using calculated EFG and CS tensors for 1H, 2H, 14N and 15N via density functional theory as described in 2.1.1 Hydrogen.18 2H NMR was examined in order to determine 1H chemical shifts in solids.25 It was shown that the sensitivity can be enhanced by applying 1H to 2H cross polarization and by adding spinning-sideband spectra, then 2H natural-abundance MAS spectra revealing highly resolved 2H signals can be obtained. The second-order quadrupole eﬀects of 2H were also studied. 2.1.3 Tritium (3H) (I =1/2). The structure of complex 3H-labeled molecules was understood by complete assignment of their 1H and 3H solution-state NMR spectra with the aide of the detection of heteronuclear chemical shift correlations between 1 H and 3H nuclei.26 Heteronuclear correlation (HETCOR) experiments were demonstrated for 1H–3H systems and 2nd HETCOR experiment using the heteronuclear Overhauser eﬀect to obtain through-space correlations between nearby nuclei was also made. The experiments were used to analyze 3H incorporation in sub-milligram quantities of 3H-labeled pharmaceutical derivatives. The (N-CHDT)(a)-isosparteinium ditosylamide >I N-(SO2C6H4Me-4)2] was studied by 3H NMR spectroscopy to assign the conﬁguration of an intact stereogenic Me group.27 It was found that the S-CHDT group has a 3H chemical shift that is 49 ppb downﬁeld of the R-CHDT resonance. The sign and magnitude of this chemical shift diﬀerence of these diastereotopic tritium nuclei were found to be in agreement with predictions obtained by ab initio calculations. 2.1.4 Lithium (6,7Li) (I = 1, 3/2). High-resolution solid-state 7Li NMR was used to characterize the structure and dynamics of lithium ion transport in monoclinic Li3V2(PO4)3 and three resonances were clearly resolved and assigned to the three kinds of crystallographic sites.28 The Li[Ni1/3Mn1/3Co1/3]O2 samples prepared under six diﬀerent conditions were compared using high-resolution solid-state 6Li NMR.29 It was established that chemical shift trends to high frequency with decreasing degrees of disorder among this family of samples and this was explained according to the orbital overlap experienced by Li nuclei in the two environments. The local ordering observed in the dominant NMR resonance of Li is pervasive aﬀecting the majority of the NMR nuclei. The condensation of BuLi on o-tolualdehyde in the presence of a chiral 3-aminopyrrolidine Li amide was studied by 6Li NMR.30 The interaction between a mixed aggregate and the aldehyde was discussed on the basis of a theoretical analysis of the solvation energies of the two Li atoms by three diﬀerent ethers. The CP NMR experiments with spin state mixing under radio frequency irradiation and MAS were made for glasses in the system [(Li2O)x (Na2O)1x]0.3[B2O3]0.7 to discriminate between alkali ions by virtue of diﬀerent heteronuclear 7Li–23Na dipole–dipole coupling strengths.31 Cation–cation interactions play a signiﬁcant role in shaping the nonlinear compositional dependence of ionic condition (mixed-alkali eﬀect: MAE) in glassy solid electrolytes. Mesoporous titanium oxide treated with 0.2, 0.6 and 1.0 equiv of Li- or Na-naphthalene were characterised by solid-state 23Na and 7Li NMR spectroscopy.32 23Na NMR spectra indicated that the relative population of the framework site increases with increased reduction levels and 7Li NMR spectra display a single broad resonance, which increases in breadth with increased reduction levels. The obtained 7Li chemical suggests that an anatase-like structure with no long-range order in the least-reduced samples but a lithium titanate-like structure with no long-range order in the higher reduced materials. 2.1.5 Sodium (23Na) (I =3/2). Diphenylmethylsodium, diphenylmethylsodium and ﬂuorenylsodium were studied by 13C and 23Na solid-state NMR spectroscopy.33 Nucl. Magn. Reson., 2007, 36, 72–112 | 75 This journal is

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The chemical shifts d(13C) and d(23Na) as well as 23Na quadrupole coupling constants w(23Na) were analysed. The stability of Na+ ion complexes with 18crown-6 (18C6), dicyclohexyl-18-crown-6 (DC18C6), dibenzo-18-crown-6 (DB18C6), 15-crown-5 (15C5) and benzo-15-crown-5 (B15C5) in binary acetonitrile-dimethylformamide mixtures were monitored by 23Na NMR measurements.34 The variation of 23Na chemical shift with [crown]/[Na+] mole ratios indicates the formation of 1:1 complexes and the formation constants of the resulting complexes were evaluated. It was found that the stabilities of the complexes vary in the order 15C5 4 DC18C6 4 B15C5 4 18C6 4 DB18C6 in pure acetonitrile, while DC18C6 4 18C6 4 15C5 4 B15C5 4 DB18C6 in pure DMF. Metal-ligand complexation systems were studied NMR chemical shift titration and the results for LiClO4:12crown-4 system in acetonitrile and the NaClO4:12-crown-4 system in methanol were reported.35 Mesoporous titanium oxide treated with 0.2, 0.6 and 1.0 equiv of Li- or Na-naphthalene were characterised by solid-state 23Na and 7Li NMR spectroscopy as described in 2.1.4 Lithium.32 The dynamic behaviour of Na+ in NaCl-exchanged polyamide (PA) ﬁlms comparable to those of the active skin layer of many reverse osmosis (RO) membranes was studied by 23Na NMR spectroscopy.36 The 23Na NMR spectra for freshly made polymer samples exchanged in 1 M NaCl solution show signiﬁcant relative humidity (RH) dependence. The solution-diﬀusion model for RO membranes transport was provided and the capabilities of multi-nuclear NMR methods to investigate molecular-scale structure and dynamics of the interactions between dissolved species and RO membranes were demonstrated. The susceptibility to ischemia-reperfusion in isolated hearts from diabetic db/db and control db/+ mice was studied by 23Na and 31P NMR spectroscopies.37 The higher duration of ventricular tachycardia and the degeneration of ventricular tachycardia into ventricular ﬁbrillation were observed upon reperfusion in db/db hearts. 2.1.6 Potassium (39K) (I = 3/2). The quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) and double frequency sweep (DFS)/QCPMG pulse sequences were applied for acquiring solid-state 39K NMR spectra of organometallic complexes. Ab initio carbon chemical shielding anisotropy (CSA) calculation and 39K electricﬁeld gradient (EFG) measurements were made in order to correlate the experimental NMR parameters with the molecular. 39K DFS/QCPMG and 13C CP/MAS experiments proved invaluable for probing molecular structure, temperature-dependent structural changes and the presence of impurities in these systems.38 The eﬄux of K+ from suspensions of human erythrocytes [red blood cells (RBCs)], which is occurred in response to the calcium ionophore and calcium ions, was studied by 39K NMR and the velocity of the K+ eﬄux mediated by the Gardos channel was determined.39 Signals from the intra—and extracellular populations of 39K+ were diﬀerenciated by T1. The eﬀect of nitrate uptake on the subcellular distribution of tissue nitrate in maize root tips was investigated by 39K and 133Cs NMR.40 2.1.7 Rubidium (87Rb) (I = 3/2). A complex of 1,6-anhydro-b-maltose with rubidium and that of 1,6-anhydro-b-D-glucopyranose with rubidium were investigated by use of 87Rb NMR spectroscopy and diﬀusion-ordered NMR spectroscopy (DOSY).41 The complex formation with rubidium was identiﬁed for 1,6-anhydro-bD-glucopyranose using NMR and electrospray ionization mass spectrometry techniques. The ordered state of Na5RbCu4(AsO4) Cl2 was characterize by 87Rb NMR and the properties of Rb nuclear site and the structural phase transitions around 74 and 110 K were discussed.42 Mesoporous tantalum oxide rubidium fulleride composites were studied by solid-state 87Rb and 13C NMR.43 Solid-state 87Rb NMR experimental results indicated the presence of two Rb environments associated with the walls or channels of the mesostructure as well as several resonances associated with various fulleride species. 76 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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2.1.8 Cesium (133Cs) (I =7/2). The crystal structure and properties of lithium (cryptand[2.1.1]) ceside (Li+(C211)Cs) and cesium (cryptand[2.2.2]) ceside (Cs+(C222)Cs) were studied by 133Cs NMR and large paramagnetic chemical shifts were observed.44 Ab initio multiconﬁguration SCF calculations were also made. The eﬀect of nitrate uptake on the subcellular distribution of tissue nitrate in maize root tips studied by 39K and 133Cs NMR was described in 2.1.6 Potassium.40 2.2 Group 2 (9Be,

25

Mg,

43

Ca,

87

Sr,

137

Ba)

2.2.1 Beryllium (9Be) (I = 3/2). The interaction between a dicarboxyimidazolebased polymer and Be(II) was studied by 1H and 9Be NMR and DFT calculations.45 Diﬀerences in the binding modes of the mononuclear and polymeric species are discussed. DFT calculations using the GIAO-based method were performed on 16 cation-p complexes formed by cations of Li+, Na+, Be2+ and Mg2+, and p systems of benzene, 1,3,5-triﬂuorobenzene (TFBZ), 1,3,5-trimethylbenzene and 1,3,5-trimethoxybenzene (TMOBZ).46 The calculations revealed that the cation-p interaction has a remarkable eﬀect on NMR chemical shifts. 2.2.2 Magnesium (25Mg) (I = 5/2). The temperature dependence of 17O and Mg NMR chemical shifts in solid MgO were calculated to describe the motion of the nuclei and to compute the NMR chemical shifts, which were obtained using the gauge-including projector augmented wave method.47 The chemical shift behaviour with temperature cannot be explained by thermal expansion alone. Vibrational corrections due to the ﬂuctuations of atoms around their equilibrium position are crucial to reproduce the experimental results. 25

2.2.3 Calcium (43Ca) (I = 7/2). A correlation of the 43Ca NMR isotropic chemical shift with Ca–O distance in biomolecules was found by solid-state 43Ca NMR spectroscopy.48 The 43Ca shift increases as the mean Ca–O distance decreases, with a strong deshielding being observed for calcium with strong Ca–O bonds. 43Caenriched model slags were studied by 43Ca 3QMAS NMR spectroscopy to know the local environments of Ca2+ ions in slow- and rapid-quench slags.49 The slow-quench slag has well-deﬁned CaO8 polyhedra in a crystalline form, while the rapid-quench slag may have CaO6 octahedral species. 2.2.4 Strontium (87Sr) (I = 9/2). Powder samples possessing either simple cubic (SrO) or ﬂuorite-analog (SrCl2 and SrF2) structures were studied by 87Sr MAS NMR.50 The MAS spectra of these samples reveal a sideband pattern resulting from ﬁrst order quadrupolar broadening of the outer transitions brought about by imperfections in the crystal structure. The chemical sifts for SrO, SrCl2 and SrF2 were discussed. The Sr sites in the natural minerals strontianite (SrCO3) and celestine (SrSO4) were characterised by using quadrupolar Carr-Purcell-Meiboom-Gill (QCPMG) pulse sequence.51 The quadrupolar parameters of 87Sr obtained by simulations of the experimental spectra appear to be highly sensitive to the symmetry of the Sr coordination environment. A fully strontium-exchanged synthetic mica of Na4Mg6Al4Si4O20F4 was studied by solid-state 87Sr NMR and 87Sr NMR spectrum of the heat-treated mica shows a single strontium environment with a quadrupolar coupling constant of 9.02 MHz and a quadrupolar asymmetry parameter of 1.0.52 The strontium cations in the proton-free interlayer are bound through electrostatic interactions as nine coordinate inner-sphere complexes sitting in the ditrigonal holes. The results demonstrated that structural details of strontium binding by phyllosilicate minerals are provided by modern pulsed NMR techniques and high ﬁelds. SrTinO3 (n = 16, 18) was measured by 87Sr quadrupole perturbed NMR spectroscopy and this showed that local symmetry breaking takes place at the A site of the ABO3 perovskite lattice in the cubic phase and not only at the B site.53 The start of Nucl. Magn. Reson., 2007, 36, 72–112 | 77 This journal is

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the antiferrodistortive transition around Ta = 105 K is accompanied by a large splitting of the 87Sr NMR line due to formation of macroscopic 901 domains and an anomalous shortening of the T2 of the quadrupole satellite transitions. 2.2.5 Barium (137Ba) (I = 3/2). The eﬀect of the particle size of BaTiO3 and PbTiO3 on the material properties was investigated 137Ba NMR spectroscopy and typical changes in the ﬁne structure tensor and the quadrupole coupling tensor were observed.54,55 The structure model for very small grains in the ferroelectric tetragonal phase was proposed. 2.3.

Group 3 (45Sc,

89

Y,

139

La,

171

Yb,

235

U)

2.3.1 Scandium (45Sc) (I = 7/2). Solid-state MAS and static 45Sc NMR spectroscopies, ab initio calculations and X-ray crystallography were applied to study the relationships between 45Sc NMR interactions and molecular structure and symmetry for Sc(acac)3, Sc(TMHD)3, Sc(NO3)3 5H2O, Sc(OAc)3, ScCl3 6H2O, ScCl3 3THF and ScCp3.56 These systems provide a variety of scandium coordination environments yielding an array of distinct 45Sc chemical shielding and electric ﬁeld gradient tensor parameters. The ﬁrst observations of scandium chemical shielding anisotropy were obtained from the spectra at two distinct magnetic ﬁelds. The structures of the microcrystalline Sc(OTf)3 were characterised by solid-state 45Sc, 13C and 19F NMR. 45 Sc NMR isotropic chemical shifts and quadrupole coupling constants of scandium-containing solid oxides were measured.57 The 45Sc isotropic chemical shift appears to be dominated by the ﬁrst neighbor coordination number and the diﬀerence in the isotropic shifts between six-coordinated and eight-coordinated scandium is more than 150 ppm. The chemical shift correlation was applied to (ZrO2)0.92(Sc2O3)0.08 and the mean coordination number was obtained. 2.3.2 Yttrium (89Y) (I = 1/2). [Y(CH2SiMe3)(12-crown-4)(THF)3]2+[BPh4]2 and a series of similar compounds were studied by NMR spectroscopies including 89 Y NMR.58 The 1JYC coupling constants for yttrium nuclear at the Y-CH2 group and the 89Y chemical shift values were discussed. 2.3.3 Lanthanum (139La) (I = 7/2). Solid LaIII coordination compounds were measured by 139La NMR at applied magnetic ﬁelds of 11.75 and 17.60 T.59 The values obtained by the 139La NMR measurements were as follows: the 139La quadrupolar coupling constants range from 10.0 to 35.6 MHz, the spans of the chemical shift tensor range from 50 to 260 ppm and the isotropic chemical shifts range from 80 to 178 ppm. The breadth and shape of the 139La NMR spectra of the central transition are dominated by the interaction between the 139La nuclear quadrupole moment and the electric ﬁeld gradient. Magnetic-shielding tensors, which was calculated by using relativistic zeroth-order regular approximation density functional theory (ZORA-DFT) and incorporating scalar only or scalar plus spin-orbit relativistic eﬀects, reproduce the experimental chemical shift tensors. Results from a solid-state 139La NMR spectroscopic measurements of the anhydro lanthanum(III) halides (LaX3, XQF, Cl, Br and I) were reported and the 139La quadrupolar coupling constants were found to range from 15.55 to 24.0 MHz for LaCl3 and LaI3, respectively.60 The lanthanum isotropic chemical shifts exhibit an inverse halogen dependence and the spans of the magnetic shielding tensors vary widely. DFT calculations of the 139La electric ﬁeld gradient and magnetic shielding tensors were also made. LaHx (2.0 r x r 3.0) samples were characterised by 139La NMR spectroscopy and the temperature and composition dependence of all quantities was determined.61 The chemical shift is larger than the Knight shift for 139 La in the LaHx samples. It was found by 139La- and 55Mn NMR measurements 78 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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that the ground state of the A-site-ordered perovskite manganite LaBaMn2O6 is a spatial mixture of the ferromagnetic and antiferromagnetic regions.62 2.3.4 Ytterbium (171Yb) (I = 1/2). Charge ordering of Yb ions in the quantum spin chain system Yb4As3 was studied by 171Yb NMR and the clear evidence for the existence of 4f holes on Yb2+ sites was obtained from the non-monotonic T-dependence of the resonance shift K.63 2.3.5 Uranium (235U) (I = 7/2). 235U antiferromagnetic NMR (AFNMR) signal was resolved by using 235U-enriched samples of USb2.64 The U hyperﬁne ﬁeld and coupling constant were estimated for USb2. The chemical shifts of UF6nCln were investigated by 235U and 19F NMR and DFT calculation and 235U NMR shieldings was also calculated.65 2.4 Group 4 (47,

49

Ti,

91

Zr)

47, 49

Ti) (I = 5/2, 7/2). The separation of the spectroscopic 2.4.1 Titanium ( contribution from both 47Ti and 49Ti in solid-state NMR spectra was reported for TiO2 polymorphs as anatase and rutile.66 The separation of the two isotopes for anatase at high ﬁeld facilitated accurate determination of the electric ﬁeld gradient and chemical shift anisotropy tensors. The rutile sample was measured by 49Tiselective NMR at diﬀerent magnetic ﬁelds and the spectra with diﬀerent scalings of the two anisotropic tensors were obtained. A small chemical shielding anisotropy (CSA) of 30 ppm was also determined. 2.4.2 Zirconium (91Zr) (I = 5/2). The crystalline phase of ZrSiO4 was studied by 29Si, 17O and 91Zr NMR and computational calculation.67 The NMR spectra were calculated by means of ﬁrst principles density functional methods to ﬁnd an additional evidence for the presence of high concentrations of defects in irradiated zircon. The inﬂuence of the substitution pattern on steric and electronic parameters for a series of borazirconocenophanes in the Ziegler-Natta ethene polymerisation behaviour was studied by 91Zr NMR spectroscopy and X-ray diﬀraction analyses.68 The stability of the species after activation was also studied by aging and interrupting the polymerisation and borazirconocenophanes proved to form a stable species after activation with MAO. It was shown that an application of 47Ti, 49Ti and 91Zr NMR is extremely useful in controlling the microscopic structure of semi-Heuslertype intermetallics for TiPtSn, ZrPtSn, HfPtSn and ThPtSn.69 However, no valuable information on structural order/disorder in MPtSn compounds can be directly obtained from static NMR spectra of 117Sn, 119Sn and 195Pt nuclei. Since the observed spectra are broadened far beyond the rigid-lattice dipolar width due to indirect spin couplings of these heavy nuclei through the chemical bondings. 2.5 Group 5 (51V,

93

Nb)

51

2.5.1 Vanadium ( V) (I = 7/2). A single crystal of b-Na0.33V2O5 was measured by 51V NMR to study the local magnetic susceptibility and the electronic structure at the vanadium sites.70 The 51V Knight shift and the electric ﬁeld gradient tensors at the vanadium sites were determined and the temperature dependence of principal components of the 51V Knight shift and the electric ﬁeld gradient tensors were also obtained. The orbital ordering of Lu2V2O7 was investigated by 51V NMR measurements and a characteristic angle dependence reﬂecting V 3d orbital states was found.71 It was found by the temperature dependence of the NMR spectra that the magnitude of the quadrupole moment is almost invariant below TC and that the orbital ordering would probably persist above TC. A 1-dimensional Heisenberg antiferromagnet LiCuVO4 was studied by 7Li and 51V NMR and both the results Nucl. Magn. Reson., 2007, 36, 72–112 | 79 This journal is

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were compared to theoretical predictions.72 The 51V solid-state NMR spectroscopy for the 67.5 kDa vanadium chloroperoxidase was performed and the quadrupolar and chemical shift anisotropy tensors were determined by simulations of the spinning sideband envelopes and the line shapes of the individual spinning sidebands corresponding to the central transition.73 With the quadrupolar coupling constant Cq of 10.5 1.5 MHz and chemical shift anisotropy Ds of 520 13 ppm, the information on the geometric and electronic structure of the vanadium center was obtained. The quasi-one-dimensional BaCu2V2O8 was studied by 51V NMR measurements and the two 51V NMR lines that are associated with two vanadium crystallographic sites were resolved.74 The temperature-dependent NMR shift for each site shows low-dimensional magnetism with a broad maximum at Tmax. The NMR chemical shifts and spin-lattice relaxation rates below Tmax indicate activated behaviour conﬁrming the spin gap formation in BaCu2V2O8. The BixV8O16 (1.72 r x r 1.80) that shows a temperature-induced metal-insulator transition (MIT) was studied by 51V NMR.75 Observation of the 51V-NMR signal below the MIT temperature (TMIT) indicates the existence of non-magnetic V sites and the decrease in the Knight shift at low temperatures suggests the spin-singlet nature of the ground state. 2.5.2 Niobium (93Nb) (I = 9/2). The 93Nb solid-state NMR spectra of a series of inorganic niobates with Nb in diﬀerent oxygen coordination environments were measured and their chemical shielding and quadrupole tensor parameters were determined using conventional and ultrahigh speed MAS, DQ STMAS, solid-echo NMR and computer simulation.76 It was demonstrated that the 93Nb isotropic chemical shift is sensitive to the coordination number of Nb sites. The possible correlation between the value of the isotropic chemical shift and the ionic character of the NbOx–MOy polyhedra association was suggested. A mixed KTa1xNbxO3 single crystal with x = 15% was measured by 93Nb NMR and an unresolved quadrupole-induced 1st-order satellite background was observed.77,78 It demonstrates that the Nb ions occupy oﬀ-center positions rather than the high symmetry central perovskite site. Half-sandwich niobium metallocenes Cp 0 Nb(I)(CO)4 and CpNb(V)Cl4 (Cp = C5H5 and Cp 0 = C5H4R with R = COMe, CO2Me, CO2Et and COCH2Ph) were studied by solid-state 93Nb and 13C NMR, in combination with theoretical calculations of NMR tensors.79 Anisotropic quadrupolar and chemical shielding parameters were estimated from 93Nb MAS and static NMR spectra for seven diﬀerent complexes. The calculated chemical shielding parameters and electric ﬁeld gradient tensors were used to determine relations between tensor orientations, the principal components and molecular structures for the niobium metallocenes. 2.6 Group 6 (53Cr,

95,97

Mo,

183

W)

2.6.1 Chromium (53Cr) (I = 3/2). The 53Cr chemical shifts of CrO42, Cr2O72, CrO3X, CrO2X2 (X = F, Cl) and Cr(CO)5L (L = CO, PF3, CHNH2, CMeNMe2) were calculated, using geometries optimized with the gradient-cor. BP86 density functional, at the gauge-including AOs (GIAO)-, BPW91- and B3LYP levels and comparing with those obtained by 53Cr NMR experiments.80 For selected cases, 53Cr NMR line widths can be rationalized in terms of electric ﬁeld gradients computed with the BPW91 or molecular correlation times. The 53Cr chemical shifts and electric ﬁeld gradients were predicted for CrO3, Cr(C6H6)2 and Cr(C6H6)CO3 and for Cr2(m2-O2CH)4 with reduced reliability. The behaviour that ferromagnetic ordering temperature of SrRu1xCrxO3 increases to 175 and 186 K for x = 0.05 and 0.12, respectively, from 162 K for SrRuO3 (x = 0) was investigated by 53Cr and 99, 101Ru NMR. The study revealed that Cr is in a ‘valence state’ of Cr3+ (t2g3m), and Ru is in a mixed valence state of Ru4+ (t2g3m1k) and Ru5+ (t2g3m).81 80 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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2.6.2 Molybdenum (95, 97Mo) (I = 5/2, 5/2). Photolysis of Mo(CO)6 in nheptane Solution with Et2SiH2 was studied by 1H, 29Si and 95Mo NMR spectroscopy.82 The 95Mo NMR spectrum showed a resonance at d = 3785 at high ﬁeld, which is characteristic for seven-coordinate molybdenum compounds. The diamagnetic octacyanomolybdate(IV) anions, Mo(CN)84, of approximately dodecahedral and square antiprismatic symmetry were investigated by solid-state 95Mo NMR spectroscopy.83 Quantum chemical calculations of the Mo s and EFG tensors, using zeroth-order regular approximation density functional theory and RHF methods, were carried out and the results were compared with those obtained by the experiments. 95Mo quadrupole couplings in molydbates were measured by MAS NMR and ab initio density functional theory calculations of the electric ﬁeld gradient were also performed.84 It was predicted that 95Mo MAS NMR could evolve as a routine characterization tool for ill-deﬁned structures such as supported molybdates in catalysis when the experiments would be made 417 T. The (A, A 0 )2FeMoO6 (A, A 0 = Ca, Sr, Ba) ferromagnetic oxides with double perovskite structure were studied by 95, 97Mo and 57Fe NMR spectroscopy.85 The NMR experiments provided clear evidence that the magnetic moment at Mo sites is not constant but varies sensitively with the size of the ions and the 95, 97Mo frequency and the electronic charge at Mo ions are smaller in Ba and Ca than in Sr-based oxides. 2.6.3 Tungsten (183W) (I = 1/2). A phosphane sulfate relativistic DFT method was employed to calculate the 183W and 17O NMR chemical shifts for large polyoxotungstates, such as W6O192, CH3OTiW5O183, W5O18WIINO3, W10O324, a-d-g-XW12O40n, b-PW9O28Br63, P2W18O626, PW2O143 and W7O246.86 The analysis of the components of the paramagnetic shielding showed that the most signiﬁcant change in both 183W and 17O NMR chemical shifts for anions consisting of tungsten and oxygen atoms are the occupied-occupied and not the occupied-virtual ones. The same authors also studied W5O18WIINO3, g-SiW12O406, P2W18O628 and W10O326 by the same methods.87 2.7 Group 7 (55Mn,

99

Tc)

55

2.7.1 Manganese ( Mn) (I = 5/2). Bi0.125Ca0.875MnO3 and CaMnO3 were studied by 55Mn NMR measurements and NMR signals observed at 4.2 K for Bi0.125Ca0.875MnO3 around 100 and 605 MHz were ascribed to regions with ferromagnetic spin structure from their behaviour in external magnetic ﬁelds.88 La2/3Ca1/3MnO3 epitaxial ﬁlms on (001) and (110) SrTiO3 substrates were measured by 55Mn NMR and it was shown that the (110) ﬁlms do not show traces of electronic phase separation, in contrast to (001) ﬁlms.89 The results provided evidence that no weakening of double exchange coupling at interfaces takes place in (110) ﬁlms. A single crystal of YMn4Al3 was studied by using 55Mn and 27Al NMR measurements. Two sets of NMR resonance peaks were assigned to the respective Al sites based on the diﬀerence in NMR shift, linewidth and relaxation rates.90 NMR shift and linewidth for 55Mn and 27Al NMR follow temperature dependence of the susceptibility, conﬁrming that the hyperﬁne ﬁeld from Mn 3d spins dominates local electronic structures at both Al and Mn sites. The Mn12 single-molecular magnet (SMM) in truly axial (tetragonal) symmetry and the complex [Mn12O12(O2CCH2Br)16(H2O)4] 4CH2Cl2 (2 4CH2Cl2 or Mn12–BrAc) was studied by 55Mn NMR spectroscopy and the quadrupole coupling parameters (e2qQ) was determined.91 It was found that crushing crystals of Mn12–BrAc into a microcrystalline powder causes severe broadening and shifts of the NMR resonances. La0.67Sr0.33MnO3 thin ﬁlms were studied by 55Mn NMR and two distinct lines were observed at 322 and 380 MHz corresponding to the interface with localized charges and to the ﬁlm bulk with itinerant carriers.92 The ﬁeld dependence of the NMR signal intensity above the eﬀective anisotropy ﬁeld agrees with a model of Nucl. Magn. Reson., 2007, 36, 72–112 | 81 This journal is

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magnetically homogeneous sample. La0.7Sr0.3MnO3 particles were studied by 55Mn NMR and temperature dependences of the NMR spectra to understand the magnetic properties of its ﬁne-particle ensembles.93 The low-temperature blocking of its magnetic moments was clearly observed and it was found that the blocking temperature depends on the measuring frequency. La0.67Ca0.33Mn0.9757Fe0.03O3 was measured by means of zero ﬁeld 55Mn and 57Fe NMR and it was found that the 55 Mn NMR spectra exhibit a single double exchange line up to the magnetic ordering temperature.94 Application of a molecular ﬁeld model to the temperature dependence of the 55Mn and 57Fe hyperﬁne ﬁeld allows to estimate values of the Mn–Mn and the Fe–Mn exchange integrals. The 55Mn NMR study of the La0.75Sr0.25MnO3 particles was reported and a dominant signal from the double exchange controlled metallic ferromagnetic interior of the grains and a small signal from insulating ferromagnetic regions were observed.95 The double exchange line in the NMR spectrum shows a frequency shift with applied ﬁeld according to a full 55 Mn gyromagnetic ratio. La0.6Sr0.3Mn1.1xFexO3d(x = 0, 0.04) samples were studied by 55Mn NMR.96 Their broad asymmetric 55Mn NMR spectra support the high-frequency electron-hole exchange between Mn3+ and Mn4+ and the fact that their environments are diﬀerent due to a high defect concentration and high structural inhomogeneity. The single crystal 55Mn NMR studies of Mn12O12(CH2BrCOO)16(4H2O)-4CH2Cl2 indicate that the highly symmetric lattice may be an improved model for studying single-molecular magnetism.97 The 55Mn NMR spectra from single crystal yield much-enhanced NMR data such as 55Mn hyperﬁne and quadrupole couplings as compared to magnetically oriented powders. The single crystals of [Mn12O12(O2CMe)16(H2O)4]-2MeCO2H-4H2O and [Mn12O12(O2CCH2Br)16(H2O)4]-4CH2Cl2 were studied by 55Mn NMR spectroscopy and their single crystal spectra gave a dramatic improvement in the spectral resolution over oriented powder spectra, allowing the determination of quadrupole coupling parameters.98 2.7.2 Technetium (99Tc) (I = 9/2). Time-dependent analyses of the formation reactions of mixed dicarbonyl-mononitrosyl complexes from the organometallic precursor, [MX3(CO)3]+, (M = 99Tc, X = Cl, Br) by 99Tc NMR spectroscopy and HATR-IR were made and it was revealed that the almost quantitative substitution of one CO ligand by NO+ is caused and (NEt4)[TcCl3(CO)2NO] and [TcCl (m-Cl)(CO)2NO]2 are produced.99 The isolated complexes and their potential facial isomers were further investigated by DFT calculations. The 99Tc NMR data for Tc compounds in various oxidation states are summarized in a review.100 2.8 Group 8 (57Fe,

99

Ru)

57

2.8.1 Iron ( Fe) (I = 1/2). The intramolecular dynamic behaviour of the tetrahedron-type cluster [Fe2(CO)6(m-SNH)] was studied by 13C NMR spectroscopy, and the 57Fe chemical shift and the coupling constants J(57Fe,13C) were measured.101 Density-functional-based Car-Parrinello and Born-Oppenheimer molecular dynamics simulations were presented for ferrocene, FeCp2 and its protonated form, FeCp2H+, in the gas phase, employing BP86 and B3LYP functionals, and thermally averaged chemical shifts were computed from snapshots along the trajectory, where 1 H and, in particular, 57Fe chemical shifts in FeCp2H+ are sensitive to the location of the proton.102 2.8.2 Ruthenium (99Ru) (I = 3/2). The computed chemical shifts of transitionmetal complexes with dimetridazole (=1,2-dimethyl-5-nitro-1H-imidazole; (1), a prototypical nitro-imidazole-based radiosensitizer, were reported at the GIAOBP86 and -B3LYP levels for BP86/ECP1-optimised geometries, and the 195Pt chemical shifts of cis- and trans-[PtCl2(1)2] are well-reproduced using the zero-order 82 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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regular approximation including SO coupling (ZORA-SO), and predictions are also reported for 99Ru and 103Rh chemical shifts, which suggest that these metal centers could be used as additional, sensitive NMR probes in their complexes with nitroimidazoles.103 2.9 Group 9 (59Co,

103

Rh)

2.9.1 Cobalt ( Co) (I = 7/2). 59Co chemical shifts were computed at the GIAOB3LYP level for [Co(CN)6]3, [Co(H2O)6]3+, [Co(NH3)6]3+ and [Co(CO)4] in water.104 A chemical shielding calculation using density functional theory at the BP86/AE1 level was presented for the Co bis(dicarbollide) ion [3-Co-(1, 2C2B9H11)2] (1) and selected isomers and rotamers thereof.105 The synthesis and characterisation (X-ray crystallography, UV/visible spectroscopy, electrochemical, ESI-MS and 1H, 13C and 59Co NMR) of [Co(L)(O2CO)]ClO4 xH2O (L = tpa = tris(2-pyridylmethyl)amine (x = 1), pmea = bis((2-pyridyl)methyl)-2-((2-pyridyl)ethyl)amine (x = 0), pmap = bis(2-(2-pyridyl)ethyl)(2-pyridylmethyl)amine (x = 0), tepa = tris(2-(2-pyridyl)ethyl)amine (x = 0)) which contain tripodal tetradentate pyridyl ligands and chelated carbonate ligands are reported.106 59

2.9.2 Rhodium (103Rh) (I = 1/2). Using 103Rh[1H] cross-polarisation (CP) methods, solid-state 103Rh NMR spectra for diamagnetic Rh(III) compounds were obtained, and the isotropic chemical shift and chemical shift anisotropy (CSA) are reported for a crystalline form of the dihydroxy-bridged Rh(III) dimer and for a salt of the oxo-centered acetate-bridged Rh(III) trimer, from analysis of conventional CP/MAS spectra.107 2.10 Group 10 (195Pt) 2.10.1 Platinum (195Pt) (I = 1/2). Variable low-frequency 15N coordination shifts (ca. 70–140 ppm) were noted for a number of chloride complexes of Pd(II), Pt(II), Au(III), Pd(IV), Pt(IV), Co(III), Rh(III) and Zn(II) with pyridine, 2, 2 0 -bipyridine, 1, 10-phenanthroline, 2, 2 0 -biquinoline, purine and 1, 2, 4-triazolo-[1, 5a]-pyrimidine(s), and some dependencies between the magnitude of the shielding eﬀect and such features of the concerned complex as the type of central ion, its electron conﬁguration (oxidation state) and the coordination sphere geometry were discussed.108 195Pt chemical shifts and 1JPtPt coupling constants were measured for a series of head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) dinuclear complexes involved in the axial water substitution reactions with halide ions (X = Cl, Br): HH-[Pt2(NH3)4(m-amidato)2L1L2]n+, [L1Pt(N2O2)-Pt(N4)-L2]n+ (amidato = alpha-pyridonato, alpha-pyrrolidonato and pivalamidato) and HT-[Pt2(NH3)4(mu-alpha-pyridonato)2L1L2]n+, [L1-Pt(N3O)Pt(N3O)-L2]n+; the diaqua (L1, L2 = H2O, n = 4), the aquahalo (L1 = X, L2 = H2O, n = 3) and the dihalo complexes (L1, L2 = X, n = 2).109 A new approach by chemometrics in order to build a model to predict the chemical shift of a Ptcomplex on the basis of its molecular features was presented using an artiﬁcial neural network algorithm, and was successfully applied such a model to 185 diﬀerent 195Pt chemical shift values.110 The reactions of [Pt(NH3)2(NHCOtBu)2] and TlX3 (X = NO3, Cl, CF3CO2) yielded dinuclear [{Pt(ONO2)(NH3)2(NHCOtBu)}Tl(ONO2)2(MeOH)] (2) and trinuclear [{PtX(RNH2)2(NHCOtBu)2}2Tl]+ [X = NO3 (3), Cl (5), CF3CO2 (6)], which were spectroscopically and structurally characterised, and strong Pt–Tl interaction in the complexes in solutions was indicated by both 195Pt and 205Tl NMR spectra.111 Some basic theoretical aspects of 195Pt NMR spectroscopy and also the empirical approach used by the researchers in the ﬁeld were brieﬂy reviewed.112 Density functional theory using the zero-order regular approximately two-component relativistic Hamiltonian was applied to calculate the 195Pt chemical shifts for [PtCl6]2, [PtCl4]2 and [Pt2(NH3)2Cl2(Me3Nucl. Magn. Reson., 2007, 36, 72–112 | 83 This journal is

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CCONH)2(CH2COCH3)]Cl.113 Pd and Pt chloride complexes with pyridine (py), 2, 2 0 -bipyridine (bpy) and 1, 10-phenanthroline (phen), trans-/cis-[M(py)2Cl2], [M(py)4]Cl2, trans-/cis-[M(py)2Cl4], [M(bpy)Cl2], [M(bpy)Cl4], [M(phen)Cl2], [M(phen)Cl4], where M = Pd, Pt, was studied by 1H, 195Pt and 15N NMR.114 The computed chemical shifts of transition-metal complexes with dimetridazole (=1,2dimethyl-5-nitro-1H-imidazole; 1), a prototypical nitro-imidazole-based radiosensitiser, were reported at the GIAO-BP86 and -B3LYP levels for BP86/ECP1-optimised geometries, and the 195Pt chemical shifts of cis- and trans-[PtCl2(1)2] are wellreproduced using the zero-order regular approximation including SO coupling (ZORA-SO), and predictions are also reported for 99Ru and 103Rh chem. shifts, which suggest that these metal centers could be used as additional, sensitive NMR probes in their complexes with nitro-imidazoles.115 Cis-Pt(amine)2I2 were transformed into the iodo-bridged dimers, which were characterised mainly by multinuclear (195Pt, 1H and 13C) magnetic resonance spectroscopy.116 The ZORA spinorbit Hamiltonian, in conjunction with the gauge including orbital (GIAO) method based on DFT theory was used to calculate 195Pt chemical shift of 195PtClxBr6x2 complexes.117 In the solid state, heavier NMR-active nuclei such as 195Pt, 199Hg and 207 Pb commonly exhibit chemical shifts that range well over 1000 ppm, depending upon the orientation of the mol. within the applied magnetic ﬁeld. Thus, acquiring NMR spectra of polycrystalline samples is often an experimental challenge because of these very broad powder patterns. In acquiring chemical shift powder patterns of these nuclei, the authors provide several examples that demonstrate that a considerable saving in time is realised by using the CPMG experiment as opposed to the standard 1-pulse or spin-echo experiment.118 2.11 Group 11 (63Cu,

107,109

Ag)

63

2.11.1 Copper ( Cu) (I = 3/2). Polycrystalline tetra-nuclear Cu4[S2P(O-iC3H7)2]4, hexa-nuclear Cu6[S2P(OC2H5)2]6 and octa-nuclear Cu8[S2P(O-iC4H9)2]6(S) complexes were synthesised and analysed by means of solid-state 31P CP/MAS and 65Cu static NMR spectroscopy, and the symmetries of the electronic environments around each P-site were estimated from the 31P chemical shift anisotropy (CSA) parameters.119 Polycrystalline tetra-nuclear Cu4[S2P(O-iC3H7)2]4, hexa-nuclear Cu6[S2P(OC2H5)2]6 and octa-nuclear Cu8[S2P(O-iC4H9)2]6(S) complexes were synthesised and analysed by means of solid-state 31P CP/MAS and 65Cu static NMR spectroscopy. 2.11.2 Silver (107,109Ag) (I = 1/2, 1/2). Formation of silver eta 2-alkyne and sigma-alkynyl complexes was detected in situ in reaction of silver triﬂate with 1hexyne in the presence of a tertiary amine by 1H, 13C and 109Ag NMR spectra.120 109 Ag solid state magic angle spinning (MAS) NMR spectra for diﬀerent silver oxides, binary as well as ternary were presented and the chemical shift of Ag nuclei is strongly dependent on the Ag oxidation state in these compounds and can thus serve as means to identify the Ag oxidation state in new materials.121 The quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) pulse sequence has received much attention in the recent literature for use in the rapid acquisition of solid-state NMR spectra of half-integer quadrupolar nuclei. Herein the authors investigate the application of the CPMG pulse sequence to enhance the signal-to-noise ratio in the static NMR spectra of spin-1/2 nuclei. The CPMG and CP/CPMG pulse sequences are applied to a series of diﬀerent NMR nuclides, including 113Cd, 199Hg, 207Pb, 15N and 109Ag.122 2.12 Group 12 (67Zn,

111,113

Cd,

199

Hg)

2.12.1 Zinc ( Zn) (I = 5/2). Quantum chemical methods to predict 67Zn NMR chemical shifts as well as quadrupole coupling constants in a series of biomimetic and inorganic zinc complexes were used, and the 67Zn NMR shifts in a series of 67

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complexes containing N,O ligands are, in general, highly correlated with the number of oxygen ligands.123 2.12.2 Cadmium (111,113Cd) (I = 1/2, 1/2). The synthesis and characterisation by solid-state 111Cd NMR of Cd(2,3-), Cd(2,4-), Cd(2,5-) and Cd(2,6-pyridinedicarboxylato) xH2O was reported.124 Cadmium(II) complexes of imidazolidine-2-selenone (ImSe) and its derivatives, Cd(1-RImSe)2Cl2 (R = Me, Et, Pr, i-Pr) and Cd(Diaz)Cl2 (Diaz = 1,3-diazinane selenone) were prepared and characterised by elemental analysis, IR and NMR (1H, 13C, 77Se and 113Cd) spectroscopy.125 2.12.3 Mercury (199Hg) (I = 1/2). Complexation behaviour of thiacrown ligands and related macrocycles towards the heavy metal ion mercury(II) was discussed using multinuclear NMR data on the complexes, with a particular attention to 199Hg NMR, and correlations between the ligand environment around the Hg(II) ion and 199 Hg NMR chemical shifts were seen.126 Investigation of the solution-state coordination chemistry of mercury was carried out using 199Hg NMR.127 Mercury(II) complexes with L-cysteine (H2Cys) in alkaline aqueous solutions were structurally characterised by means of extended X-ray absorption ﬁne structure (EXAFS) spectroscopy, Raman, 199Hg NMR.128 Measurements of 199Hg NMR chemical shift data for a series of homoleptic Hg(II) complexes with thiacrown ligands and related aza and mixed thia/aza macrocycles were ﬁrstly reported, and in mercury(II) complexes containing trithiacrown through hexathiacrown ligands, 199Hg NMR chemical shifts in the range of 298 to 1400 ppm were observed.129 The solvation of the mercury(II) ion in solvents with diﬀerent solvation properties, water, dimethylsulfoxide, N,N-dimethylthioformamide and liquid ammonia, was studied by means of 199Hg NMR, and the 199Hg chemical shift shows a pronounced dependence on the coordination number of the mercury(II) ion in the solvates resulting in a diﬀerence of over 1200 ppm between basically tetrahedral and octahedral complexes.130 The CPMG and CP/CPMG pulse sequences are applied to a series of diﬀerent NMR nuclides, including 113Cd, 199Hg, 207Pb, 15N and 109 Ag.131 In the solid state, heavier NMR-active nuclei such as 195Pt, 199Hg and 207Pb commonly exhibit chemical shifts that range well over 1000 ppm, depending upon the orientation of the molar within the applied magnetic ﬁeld. Thus, acquiring NMR spectra of polycrystalline samples is often an experimental challenge because of these very broad powder patterns. In acquiring chemical shift powder patterns of these nuclei, the authors provide several examples that demonstrate that a considerable saving in time is realised by using the CPMG experiment as opposed to the standard 1-pulse or spin-echo experiment.132 2.13 Group 13 (11B,

27

Al,

71

Ga,

203, 205

Tl)

11

2.13.1 Boron ( B) (I = 3/2). Structural features in Pyrex was identiﬁed by high resolution 29Si, 27Al and 11B magic-angle spinning MAS NMR spectroscopic measurements at 9.4 and 19.5 T, combined with 27Al and 11B multiple-quantum MAS (MQMAS), and 11B Rotor Assisted Population Transfer (RAPT).133 11B NMR of boron interaction with mineral surfaces(boehmite, silica gel and illite) was presented.134 11B solid-state NMR was used to investigate the rhamnogalacturonan II-borate complex in plant cell walls.135 Boric acid, ‘‘carbonic’’ acid and N-containing oxyacids in aqueous solution were investigated by ab initio studies of structure, pKa, NMR shifts and isotopic fractionations.136 Structural speciation of glasses in the systems PbO–B2O3–SiO2, PbO–B2O3–Al2O3–SiO2 and PbO–Al2O3–SiO2 were studied using solid state 29Si, 27Al, 11B and 207Pb NMR and Raman spectroscopy.137 2.13.2 Aluminium (27Al) (I = 5/2). The chemical knowledge about Macrodefectfree materials was shown critically for both procedure design and exploitation, and Nucl. Magn. Reson., 2007, 36, 72–112 | 85 This journal is

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chemical shifts in both 27Al and 31P MAS NMR spectra conﬁrm Al(6)–O–P(4) crosslinking in virgin probes and indicate secondary hydrolysis during moisture uptake in domains free of cross-links.138 The structures of one synthetic and two natural chlorites of the chlinochlore type were explored using X-ray diﬀraction, Moessbauer, 29Si magic-angle spinning NMR (NMR) and 27Al 3QMAS NMR.139 The eﬀect of Na/Si on the structure of sodium silicate and aluminosilicate glasses quenched from melts at high pressure were investigated by a multi-nuclear (27Al, 23 Na, 17O) 1D and 2D solid-state NMR.140 27Al-NMR and Raman spectroscopic studies of alkaline aluminate solutions with extremely high caustic content were carried out.141 Perrhenate sodalite were synthesised and the structure was investigated by Raman spectroscopy and 29Si and 27Al MAS NMR.142 A combination of 27 Al magic-angle spinning (MAS)/multiple quantum (MQ)-MAS, 13C-1H CPMAS and 13C–{27Al} transfer of population in double-resonance (TRAPDOR) NMR were used for the structural elucidation of the aluminum alkoxides aluminum ethoxide, aluminum isopropoxide and aluminum tertiarybutoxide.143 Various 2:1 type clay minerals were activated by H2SO4 treatment and the generation of solid acidity was found to be related to the evolution of new tetrahedral Al sites showing a slightly diﬀerent 27Al MAS NMR chemical shift from the original tetrahedral Al NMR resonance.144 A new aluminophosphate (AlPO) material, EMM-3, was recently synthesised at ExxonMobil, and characterised by multinuclear (13C, 31P, 27 Al), multiﬁeld solid-state NMR, SEM and powder XRD measurements.145 Spectroscopic elucidation of a 2-isopropylmalic acid (2-iPMA)-Al(III) complex was carried out using 1H, 13C and 27Al NMR spectroscopy, diﬀusion-ordered NMR spectroscopy (DOSY) and electrospray ionisation mass spectrometry (ESI-MS).146 Anionic framework aluminophosphates, with diﬀerent Al/P ratios, were studied by various solid-state NMR techniques, including 27Al, 31P magic angle spinning (MAS), 27Al–31P cross polarisation (CP), 27Al{31P} rotational echo double resonance (REDOR), and 31P{27Al} transfer of population double resonance (TRAPDOR).147 beta-CaAlF5 was synthesised by solid-state reaction, and characterised by X-ray powder diﬀraction, EPR and 19F and 27Al solid state MAS SATRAS NMR.148 A new aluminum-hydrate species in hydrated Portland cements were characterised by 27Al and 29Si MAS NMR spectroscopy.149 In order to investigate the structural evolution around Al, pulse NMR experiments were carried out on 27Al in the Zr60Ni25Al15 metallic glass and the related crystalline compound, Zr6NiAl2.150 Complex formation between S-histidine (HHis) and aluminum(III) ion in aqueous solution was studied by potentiometric measurements, ESI-MS, 27Al and 13C NMR spectroscopy.151 The dependence of the 27Al NMR shielding on the framework Al position and on the charge compensating cation coordination and hydration was studied for MCM-58 zeolite.152 Hydrothermally stable Al-containing periodic mesoporous organosilicas with various Si/Al ratios 5.6 were easily prepared at room temperature by NH4OH-catalysed, CTAB-templated hydrolysis and condensation of 1,2-bis(triethoxysilyl)ethane and Al isopropoxide, and characterisation data with XRD, TEM, SEM, N adsorption, 29Si and 27Al MAS NMR, pyridine-TPD and hydrothermal test showed that the mesoporous materials possess wormlike channels with high textural porosity, tetrahedrally and octahedrally coordinated Al atoms in their textural structures, and weak acid sites whose contents are proportional to the amount of Al incorporated.153 The synthesis and characterisation of monomeric, oligomeric and polymeric aluminum 8-hydroxyquinolines were carried out using 27 Al NMR.154 Melt and glass structure in the Al2O3–CaO–LaPO4 system were studied by 27Al and 31P NMR, and by Raman scattering.155 Boria–Alumina Mixed Oxides prepared by a sol-gel method was characterised by 27Al and 11B MAS NMR.156 The Eﬀects of T–O–T Bond Angles on NMR Chemical Shifts in Aluminosilicates were explained by a natural bonding orbital (NBO) and natural chemical shielding (NCS) analysis.157 The experimental NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was studied from relativistic density functional calculations.158 The thermal transformation of Ba 86 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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exchanged zeolite X to celsian is studied by scopy.159

27

Al and

29

Si MAS NMR spectro-

2.13.3 Gallium (71Ga) (I = 3/2). GaN crystals doped with Mn ions were synthesised by the alkali metal ﬂux method. Mixtures of metals were premelted to form an alloy and the alloy was mixed with Na/K and heated to 800 1C under 1400 psi N2 in an Al2O3 crucible. Up to 2 mol% Mn could be incorporated into the hGaN lattice, and the products were characterised by solid state 71Ga, 69Ga, 14N NMR, magnetometry, Raman spectroscopy and powder X-ray diﬀraction.160 A strategy was demonstrated for identifying unambiguously and characterizing quantity of the eﬀects of distributions of conduction electron concentrations arising from intentional or unintentional dopants in semiconductors by 71Ga MAS NMR.161 2.13.4 Thallium (203, 205Tl) (I = 1/2, 1/2). The reactions of [Pt(NH3)2(NHCOtBu)2] and TlX3 (X = NO3, Cl, CF3CO2) yielded dinuclear [{Pt(ONO2)(NH3)2(NHCOtBu)}Tl(ONO2)2(MeOH)] and trinuclear [{PtX(RNH2)2 (NHCOtBu)2}2Tl]+ [X = NO3, Cl, CF3CO2], which were spectroscopically and structurally characterised, and strong Pt–Tl interaction in the complexes in solutions was indicated by both 195Pt and 205Tl NMR spectra.162 2.14 Group 14 (13C,

29

Si,

73

Ge,

117, 119

Sn,

207

Pb)

13

2.14.1 Carbon ( C ) (I = 1/2). Antimicrobial peptides are key components of innate immunity of all life forms. Understanding the structure activity relationship of these peptides is essential for developing them into novel therapeutics that substitutes traditional antibiotics. NMR spectroscopy can provide insights into membrane-targeting antimicrobial peptides from a variety of angles.163 XPA, a 273 amino acid protein, is involved in the early stage of the nucleotide excision repair, by which a variety of DNA lesions are removed from the genome. NMR is used to analyse the structure of the central domain of XPA, which encompasses residues 98 to 219, and contains a zinc coordinating motif. Following chemical shift assignments of the backbone and side-chain 1H, 15N and 13C nuclei, the tertiary structure was determined by multi-dimensional and multi-resonance NMR methods.164 This contribution reviews applications of NMR spectroscopy in the study of the structure and the intra- and intermolecular interactions of purine derivatives.165 Diﬀerent symmetrical substituted and cyclic dialkydithiocarbamate (R = CH3, C2H5, C3H7, i-C3H7, C4H9, i-C4H9 and R2 = (CH2)5, (CH2)6, (CH2)4O) compounds, such as tetraalkylthiuram disulﬁdes, mononuclear nickel(II), binuclear zinc(II) and heteropolynuclear complexes and their adducts (both non-solvated and solvated forms) with planar and non-planar N-donor organic bases, are prepared and studied by means of natural abundance 13C and 15N CP/MAS NMR spectroscopy. 166 Much progress in terms of sensitivity, leading to much smaller requirements of sample quantities was made by the introduction of Fouriertransform NMR, allowing for more rapid acquisition of spectra and by the construction of cryomagnets with higher ﬁelds. These techniques are essentially provided the technology to routinely record 13C-NMR spectra, and 13C chemical shifts prove to be of much use for structure identiﬁcation.167 2.14.2. Silicon (29Si) (I = 1/2). The thermal transformation of Ba exchanged zeolite X to celsian is studied by 27Al and Si MAS NMR spectroscopy.168 The structures of one synthetic and two natural chlorites of the chlinochlore type were explored using X-ray diﬀraction, magic-angle spinning NMR and Moessbauer spectroscopy. The authors report unit-cell parameters, Moessbauer isomeric shifts, 29 Si NMR chemical shifts as well as 27Al isotropic shifts and quadrupolar coupling parameters.169 A multinuclear solid-state NMR investigation of the structure of the Nucl. Magn. Reson., 2007, 36, 72–112 | 87 This journal is

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amorphous alteration products (so-called gels) that form during the aqueous alteration of silicate glasses such as are used for radioactive waste containment is reported. Two series of gels were obtained, in acidic and in basic solutions, and were analysed using 1H, 29Si and 27Al MAS NMR spectroscopy.170 A series of synthetic sodium-rich saponites and trioctahedral Na, K and Ba mica solid solutions are investigated by 29Si MAS-NMR spectroscopy.171 Na8(AlSiO4)6(ReO4)2 sodalite was synthesised using a hydrothermal method and its crystal structure was determined from Rietveld reﬁnement of experimental X-ray powder diﬀraction data. MAS NMR of 29Si and 27Al nuclei showed single intense peaks at diso = 92.4 ppm and diso = 57.5 ppm, respectively, conﬁrming the alternating Si, Al tetrahedral ordering in sodalite deduced from the structural data. Chemical shifts for 29Si and 27Al calculated using correlative structural parameters (56.6 0.8 ppm and 92.3 0.9 ppm) showed good agreement with measured data indicating the validity of data derived from the Rietveld structural reﬁnement.172 MnAPSO-34 molecule sieve was synthesised with triethylamine as the template, characterised with XRD, XRF, 31P, 27 Al and 29Si NMR and FT-IR techniques and compared with SAPO-34.173 A geopolymer material based on dehydrolyed aluminosilicate and phosphoric acid is synthesised from metakaolinite condensed with low-polymeric [PO4]3n–n tetrahedral units in phosphoric acid aqueous solution at room temperature. The material structure and geopolymerisation mechanism of the products are investigated using X-ray diﬀraction, Fourier transform IR spectroscopy and 29Si, 27Al MAS NMR.174 The authors prepared a hybrid inorganic/organic, anhydride proton-conducting polymer electrolyte (MePEG3SiO3)n. Structural characterisation of this MePEG3 polymer through 29Si NMR spectroscopy and gel-permeation chromatography indicates that the MePEG3 polymer is composed of several diﬀerent structures giving a distribution of molecular weights and silicon resonances.175 Starting from diorganodichlorosilanes and the tetradentate salen-type ligand 1 o-HO-pMeOC6H3C(Ph):N(CH2)2N:C(Ph)C6H3OMe-p-OH-o, eight hexacoordinate diorganosilanes RR 0 Si[o-O-p-MeOC6H3C(Ph):N(CH2)2N:C(Ph)C6H3OMe-p-O-o] [R, R 0 = Ph, Me (2a); Ph, Et (2b); Ph, Cy (2c); vinyl, Me (2d); Ph, vinyl (2e); Ph, Ph (2f); Me, Me (2g); –(CH2)3– (3)] are synthesised. As proven by 29Si CP/MAS spectra as well as Si chemical shift tensor calculations, in compounds 2a, 2f and 2g the Si atom is most shielded in the direction of the axially arranged Si–C bonds.176 The syntheses of the ﬁrst two disilynes were reported recently: the ﬁrst by Wiberg and co-workers, who synthesized RSiRSiR (1; R = SiMe(Si-t-Bu3)2), and the second by Sekiguchi and co-workers, who synthesised RSiRSiR (2; R = Si-i-Pr[CH(SiMe3)2]2), which was also characterised by X-ray crystallography and NMR spectroscopy. The authors report the ﬁrst detailed quantum-mechanical study of the 29Si NMR chemical shifts of disilynes, RSiRSiR, in particular those with R = H, CH3, SiH3, SiMe(SiH3)2, SiMe(SiMe3)2, SiMe(Si-t-Bu3)2 (1), Si-i-Pr[CH(SiMe3)2]2 (2).177 The 29Si chemical shifts in substituted disilynes are analysed by quantum-chemistry studies using a detailed breakdown of paramagnetic contributions into couplings of occupied and virtual canonical MOs. The results give indications of substituent eﬀects on shielding and conﬁrm the importance of energy denominators in the equation for sp in sym. substituted disilynes (H3SiSiSiSiH3 and H3CSiSiCH3) on their chemical shifts.178 The structures and isomerisation of magnesium chlorosilylenoid H2SiClMgCl are investigated by ab initio MO theory for the ﬁrst time. Based on the B3LYP/6-31G(d) optimised geometries, 29Si chemical shifts and harmonic frequencies of various structures are obtained.179 Synthesis of the 1st neutral Z6-silabenzene complexes [M(Z6-C5H5SiTbt)(CO)3] [M = Cr (2), Mo (3); Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl] was achieved by the ligand exchange reactions of [M(MeCN)3(CO)3] (M = Cr, Mo) with the kinetically stabilised silabenzene C6H5SiTbt (1). The structures of Z6-silabenzene complexes 2 and 3 were fully characterised by 1H, 13C and 29Si NMR, UV/visible and IR spectroscopic analysis.180 The dependence of the 27Al NMR shielding on the framework Al position and on the charge compensating cation coordination and hydration was 88 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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studied for MCM-58 zeolite. NMR shielding constants are calculated with the large cluster models (E20 framework tetrahedral) at the geometries optimised at the periodic DFT level, employing the PW91 exchange-correlation functional. A simple linear correlation between 29Si NMR chemical shifts and av. T–O–T angles was conﬁrmed for all-SiO2 ITQ-4.181 Intermediates formed in halogen addition (X = Br, Cl, F) to alkynes (ethyne, propyne, 2-butyne, triﬂuoromethylethyne, trimethylsilylethyne and 1-trimethylsilylpropyne) were studied computationally by MP2 at the MP2/6-311++G(3df,3pd) level and/or by DFT at the B3LYP/6-31+G(d) level. GIAO-MP2 and GIAO-DFT calculations are employed to compute NMR chemical shifts (13C, 19F and 29Si as appropriate).182 The hydration characteristics and the engineering properties of three types of eco-cement pastes, including their compressive strength, speciation, degree of hydration and microstructure, are studied and compared with those of ASTM type I ordinary Portland cement. The resultant degree of hydration and the increase in the length of the CSH gels with the curing age, are conﬁrmed by 29Si NMR techniques.183 In 13C NMR spectroscopy, there are many empirical methods for fast and exact computation of 13C chemical shifts; comparable procedures for 29Si NMR chemical shifts are not existing or are older than 20 years. On basis of the largest database of 29Si chemical shifts available, along this paper a relatively simple procedure for the similarly exact calculation of the 29Si chemical shifts of disilanes (average margin of error ca. 3.7 ppm) is given.184 Treatment of Si(TPP)Cl2 (TPP = tetraphenylporphyrinato) with 2 equiv. of Na/ Hg in THF yields the reduced porphyrin complex, Si(TPP)(THF)2, in which the porphyrin ring system has an oxidation state of 4- and the complex is antiarom. Experimental 1H and 29Si NMR chemical shifts and NICS (nucleus-independent chemical shift) calculations on a model compd. indicate a strong paratropic ring current in Si(TPP).185 The authors present the application of the magic-angle turning technique to 29Si solid-state NMR of natural abundance crystalline and amorphous solids. Correlations between the isotropic and anisotropic chemical shifts are obtained by rotation of the sample around a single axis at the magic angle.186 The reaction between transPcSiCl2 (1) and the K salts of six fatty acids (2a–2f) led to the transPcSi[OOC(CH2)nCH3]2 compounds (3a–3f), which were characterised by elemental analysis IR, UV/visible and 1H, 13C and 29Si NMR spectroscopy.187 The synthesis and isolation of 12 a-aryl, b, b 0 -disilyl-substituted vinyl cations 1b-l, 7 and 8 with the tetrakis(pentaﬂuorophenyl)borate counter anion is reported. The vinyl cations are characterised by NMR spectroscopy and are identiﬁed by their speciﬁc NMR chemical shifts (d 13C(C+) = 178.1–194.5; d 13C(Cb) = 83.3–89.9; d 13C(Cipso) = 113.6–115.2; d 29Si = 25.0–12.0), supported by density functional calculations at the B3LYP/6-311G(2d,p)//B3LYP/6-31G(d) level.188 Hartree-Fock SCF (HF-SCF) theory and the Gauge-including AO (GIAO) methods were used in the calculation of 29 Si NMR chemical shifts for ABOUT 90 units of 19 compounds of various silicate species of precursors for zeolites.189 Density functional theory at the B3LYP/6311++G(d,p) level is applied to calc. the 29Si NMR chemical shifts of a variety of organosiloxane moieties including monomers or precursors for polymerisation and representative segments of organosiloxane polymers or thin ﬁlms.190 Inorganicorganic hybrid materials produced by the sol-gel method from Si(OR)4 and R 0 xySi(OR)y (R,R 0 -CnHm groups) compounds are very interesting materials for new optical techniques. Copolymerisation of tetraethoxysilane (TEOS) and of the organic modiﬁers was studied by means of both the 29Si MAS NMR and the FTIR spectroscopy.191 Hexacoordinate triﬂuoroacetohydrazonic acid silicon O,N-dicarboxylates having bulky cyclohexyl ligand at silicon undergo dissociation one of the chelating hydrazide nitrogens rather than the dissociation of the chloride acidoligand; however, corresponding triﬂate and iodide undergo ionisation of the acidoligands. Hypercoordinate [[CF3C(O):NNMe2-kO,kN]2Si(C6H11)Cl] (3, C6H11 = cyclohexyl) undergo reversible dissociation of one of the nitrogen arm of the triﬂuoroacetohydrazonate at room temperature in solution, which results in about Nucl. Magn. Reson., 2007, 36, 72–112 | 89 This journal is

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60 ppm increase of the 29Si NMR chemical shift.192 Rice (Oryza sativa L.) is a typical silicon (Si)-accumulating plant, but the mechanism responsible for the translocation from the root to the shoot is poorly understood. In this study, the form of Si in xylem sap is identiﬁed by 29Si-NMR spectroscopy.193 It has long been recognised that the 29 Si and 27Al NMR chemical shifts for aluminosilicate crystals and glasses correlate to some extent with the T–O–T bond angle (T is the tetrahedral atom Si or Al). With increasing T–O–T bond angle, the 29Si and 27Al NMR shieldings increase and the shifts thus become more negative This result was demonstrated both experiment and through quantum computations. However, no simple qualitative explanation has ever been given for what appears to be a simple qualitative trend. The authors provide such an explanation based upon quantum calculations.194 N-Methyl-2[(trialkylsilyl)methyl]pyridinium cations [R3 = Me3 (6a), iso-Pr3 (6b), Me2(Me3C) (6c)] and 4-[(trialkylsilyl)methyl]pyridinium cations (same R3, 5a–c, respectively) were prepared and studied by using 29Si and 13C NMR and single-crystal X-ray crystallography (for 5b and 6b).195 Samples in the system Lu2xYxSi2O7 (0 r x r 2) were synthesised following the sol-gel method and calcined to 1300 1C, a temperature at which the b-polymorph is known to be the stable phase for the end-members Lu2Si2O7 and Y2Si2O7. 29Si MAS NMR spectra of the diﬀerent members of the system agree with the XRD results, showing a linear decrease of the 29Si chemical shift with increasing Y content.196 2.14.3 Germanium (73Ge) (I = 9/2). The cation capture/transport ability of diazacrowns, one with side chains containing germanium (5a), another with side chains not containing germanium (7), and 4,13-diaza-18-crown-6 (8), was found to decrease in the order 5a 4 7 4 8. Titrimetric experiment and 73Ge NMR failed to give an unequivocal rationalisation of the results.197 The authors report on the pressure-induced novel phases of ferromagnetism (FM) and superconductive (SC) in the itinerant ferromagnet UGe2 through 73Ge-NQR measurements under pressure (P). Recent advances in 73Ge NMR spectroscopy are reviewed.198 High-resolution solid-state magic angle spinning 73Ge NMR spectra of hexavalent germanium compounds, i.e. diiodogermylene and bis(1-pyrrolyl)(meso-tetraphenylporphyrinato)germanium , were determined.199 High-resolution solid-state magic angle spinning 73Ge NMR spectra of some organogermanium compounds were measured.200 2.14.4 Tin (117, 119Sn) (I = 1/2, 1/2). Novel polymeric derivatives of various average molecular weights bearing tributyltin carboxylate moieties as terminal groups were prepared by esteriﬁcation with bis(tributyltin) oxide of the corresponding poly(ethylene glycol)s functionalised with dimethylenecarboxylic end groups. Low-molecular-weight compounds were also synthesised, with the aim of investigating the inﬂuence of the polymeric chain on tin properties. As investigated by Sn NMR and Fourier transform IR, the metal center appears to be completely tetracoordinated in chloroform solution at room temperature, whereas at low temperature, the tin atom undergoes a fast exchange between intramolecular pentacoordination with the ethereal oxygen atoms and the unassociated form.201 Novel polymeric derivatives bearing tributyltin carboxylate moieties in the side chain were synthesised. The coordination at tin in solution and in the solid state was investigated by both Sn-NMR and FT-IR.202 New organotins containing the (ortho-MeEC6H4-CH2-), L, group, E = O, S, Se and CH2, will be reported. The rationale for studying such systems was to evaluate their structures with respect to the intramolecular E Sn interaction and to evaluate the role of the E group in modifying their biocidal properties. Solid state Sn NMR data and biocidal activity against a suite of bacteria will also be presented.203 1,3-dithia-2-stannacyclopentane derivatives with dialkyldithiocarbamates of the types SCH2CH2SSn[S2CNR2]Cl (I) and SCH2CH2SSn[S2CNR2]2 (II) (where R = CH3, C2H5 and –CH2–CH2–) were 90 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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synthesised by the reaction of 2,2-dichloro-1,3-dithia-2-stannacyclopentane and sodium/ammonium salts of dialkyldithiocarbamates in 1:1 and 1:2 molar ratios, respectively, in anhydrous benzene. These newly synthesised derivatives were characterised by elemental analyses, thermal as well as spectral [UV, IR and multinuclear NMR (1H, 13C and 119Sn)] studies.204 The ﬁrst isolation of diarylstannanethione (tin–sulfur double-bond compound) and diarylstannaneselone (tinselenium double-bond compound), Tbt(Ditp)SnQX (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Ditp = 2,2 0 -diisopropyl-m-terphenyl-2 0 -yl; X = S and Se) was accomplished by dechalcogenation of the corresponding highly hindered tetrachalcogenastannolanes, Tbt(Ditp)SnX(4). The 119Sn NMR of stannanethione (Tbt(Ditp)SnQS) and stannaneselone (Tbt(Ditp)SnQSe), showed only one lowﬁeld broad signal at 531 and 440 ppm, respectively, characteristic of a tricoordinated tin, and hence, the stannanethione and stannaneselone display an intrinsic nature of tin-chalcogen double-bond compounds.205 Six new derivatised deltahedral Zintl ions were synthesised by reactions between the known Zintl ions Ge(9) (n-) with the halides R(3)EX and/or the corresponding anions R(3)E(-) for EQGe or Sn. The tincontaining anions were characterised also in solutions by 119Sn NMR spectroscopy.206 A series of (salen)tin(II) and (salen)tin(IV) complexes was synthesised. All complexes were fully characterised by 1H NMR spectroscopy, mass spectrometry and elemental analysis, while some were characterised by 13C, 19F and 119Sn NMR spectroscopy.207 A series of diorganotin(IV) and dichlorotin(IV) derivatives of 4-Xbenzohydroxamic acids, [HL(1) (X = Cl) or HL(2) (X = OCH(3))] formulated as [R(2)SnL(2)] (R = Me, Et, nBu, Ph or Cl; L = L(1) or L(2)), along with their corresponding mixed-ligand complexes [R(2)Sn(L(1))(L(2))] were prepared and characterised by FT-IR, 1H, 13C and 119Sn NMR spectroscopy, mass spectrometry, elemental analysis and melting points.208 Dialkyltin(IV) and trialkyltin(IV) complexes of the deacetoxycephalo-sporin-antibiotic cephalexin [7-(d-2-amino-2-phenylacetamido)-3-methyl-3-cephem-4-carboxylic acid] (Hceph) were synthesised and investigated both in solid and solution phase. Analytical and thermogravimetric data supported, while structural information was gained by FT-IR, 119Sn Mossbauer and 1 H, 13C, 119Sn NMR data.209 2.14.5 Lead (207Pb) (I = 1/2). Metal has the power to induce biological activity by interaction with DNA by thread binding mechanism. Achieving optimal chemopreventive potency with lowest toxicity continues to be our primary goal in designing and developing lead(II) complexes of phenenthrolines and dicarboxylic acids. These complexes were characterised by chemical analysis, IR, 1H, 13C and 207Pb NMR spectral studies, X-ray powder diﬀraction, molecular weight determinations.210 Crystals of the layered metal organic framework solid Pb[B(Im)4](NO3)(nH2O) can undergo exchange of the nitrate for perrhenate, a model for pertechnetate, forming Pb[B(Im)4](ReO4). The authors can monitor this reaction by 207Pb solidstate NMR and can isolate single crystals of the resultant material through growth in the presence of an excess of perrhenate.211 Lead(II) complexes with 2,4,6-tris(2pyridyl)-1,3,5-triazine (trz) were synthesised using a direct synthetic method and characterised by IR and 207Pb NMR spectroscopy and CHN elemental analysis.212 1:1 and 1:2 lead(II) complexes with 2,9-dimetyl-1,10-phenanthroline (Dmphen), {[Pb(Dmphen)(NO3)n] and [Pb(Dmphen)2(ClO4)2]} were synthesised and characterised by CHN elemental analysis, IR, 1H NMR, 13C NMR and 207Pb NMR spectroscopy.213 Structural speciation of glasses in the systems PbO–B2O3–SiO2, PbO–B2O3–Al2O3–SiO2 and PbO–Al2O3–SiO2 were studied using solid state 29Si, 27 Al, 11B and 207Pb NMR and Raman spectroscopy.214 Lead(II) complexes with ethane-1,2-diamine (en) containing two diﬀerent anions, [Pb(en)(CH3COO)X] (X = NCS, ClO4 or NO3), were synthesised and characterised by CHN elemental analysis, IR, 1H NMR, 13C NMR and 207Pb NMR spectroscopy.215 A novel 3dimensional polymeric heteropolynuclear Na(I) Pb(II) complex containing diﬀerent Nucl. Magn. Reson., 2007, 36, 72–112 | 91 This journal is

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ligands, [NaPb(ClO4)(en)(NO2)2] was synthesised and characterised by elemental analysis, IR and 1H, 13C, 207Pb NMR spectroscopy.216 Lead(II) complexes with 2,2 0 :6 0 ,200 -terpyridine (tpy) and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (trz) ligands, [Pb(tpy)(CH3COO)2] and [Pb(trz)(CH3COO)2], were synthesised and characterised by IR, CHN elemental analysis and 207Pb NMR.217 The structure of (25–x/2) Li2O (25–x/2)Na2O xPbO 50P2O5 phosphate glasses (0 r x r 50 mol%) was investigated by Raman spectroscopy and 31P-MAS and 207Pb-VOCS NMR.218 The phase transitions of a ferroelastic CsPbCl3 single crystal grown by using the Bridgman method were studied using 133Cs and 207Pb NMR.219 A new Pb(II) complex of 2.2 0 -bipyridine (bpy), acetate and thiocyanate was synthesised and characterised by CHN elemental analysis, IR, 1H NMR, 13C NMR and 207Pb NMR spectroscopy.220 {Pb(m-Br)ArPri2}2 (1), {Pb(m-Br)ArPri2But}2 (2), Pri2Ar (Me)PbPb(Me)ArPri2 (3). {Pb(C6H4-4-But)ArPri2}2 (4), Pb(But)ArPri2 (5), [Pb(CH2C6H4-4-Pri)ArPri3](6) and [Pb(Si(SiMe3)3)ArPri3](7) were characterised with use of X-ray crystallography, 1H, 13C and 207Pb NMR and UV-Vis spectroscopy.221 Pb(II) complexes with the 4,4 0 -bipyridine (4,4 0 -bipy) ligand were synthesised and characterised by CHN elemental analysis, IR, 1H NMR, 13C NMR and 207 Pb NMR spectroscopy.222 A 207Pb spin echo signal and a 17O–207Pb spin echo double resonance signal were measured in the metallic phase of BaPb1xBixO3 oxides (x o 0.15).223 The inhomogeneous magnetic broadening of the 17O and 207Pb NMR spectra resulting from a distribution of the Knight shifts was studied in the metallic phase of BaPb1xBixO3 oxides (0 r x r 0.33).224 An attempt to prepare Ce- and La-doped SiO2–PbO glasses for applications as scintillators was realised via aerogel route. Both 207Pb and 29Si magic angle spinning (MAS) NMR were used to investigate local order and connectivity.225 Reactions of triethylmetal(IV) chlorides (for example, Et3GeCl) with sodium salts of internally functionalised oximes (for example, 2-acetylpyridyl oxime) in a 1:1 molar ratio in reﬂuxing anhydrous benzene yielded [Et3M{ON:C(R)Ar}] [where R = H, Me; M = Ge, Sn or Pb; Ar = 2C5H4N, 2-C4H3O or 2-C4H3S]. The derivatives were characterised by elemental analysis and IR and NMR [1H, 13C{1H}, 119Sn{1H} and 207Pb{1H}] spectroscopic studies.226 The quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) pulse sequence has received much attention in the recent literature for use in the rapid acquisition of solid-state NMR spectra of half-integer quadrupolar nuclei. Herein we investigate the application of the CPMG pulse sequence to enhance the signal-to-noise ratio in the static NMR spectra of spin-1/2 nuclei. The CPMG and CP/CPMG pulse sequences are applied to a series of diﬀerent NMR nuclides, including 113Cd, 199 Hg, 207Pb, 15N and 109Ag.227 New Pb(II) complexes, Pb(dmphen)X2 (X = NO3, ClO4 and CH3COO; dmphen = 2,9-dimethyl-1,10-phenanthroline), were synthesised and characterised by CHN elemental analysis, IR, 1H, 13C and 207Pb NMR spectroscopy.228 A new class of Pb(II) and Sn(II) complexes of a macrocyclic Schiﬀ base ligand containing a thiosemicarbazone moiety was prepared, [M(H2MacL2)X2], where M = Pb(II) or Sn(II); H2MacL2 = 3,4,9,10-tetraphenyl1,2,5,6,8,11-hexaazacyclododecane-7,12-dithione-2,4,8,10-tetraene; X = Cl or NO3. Thus, when the triaza-macrocycle I (H2MacL1) in EtOH reacts with CrCl3, the macrocyclic ligand H2MacL2 (II) is formed. The complexes were characterised from elemental analysis, molar conductance, magnetic susceptibility, IR, 1H NMR, 119 Sn NMR, 207Pb NMR and XRD.229 Lead ﬂuoride, a superionic conductor was prepared in its nanostructured form by Inert Gas Condensation Technique (IGCT) using an Ultra High Vacuum (UHV) chamber. Solid state 207Pb MAS NMR was carried to average out the dipolar interaction and the resultant isotropic peaks were assigned to the corresponding phases.230 The results of the extensive investigations of the variation of the EPR and 207Pb NMR spectra of active centers due to the existence of the native defects generated by disorder in the IV–VI semiconductor matrixes are presented.231 The 207Pb static, magic-angle spinning (MAS) and two-dimensional phase-adjusted spinning sidebands (2-dimensional-PASS) NMR experiments were performed on (1–x)PMN/ 92 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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xPSN [where PMN stands for Pb(Mg1/3Nb2/3)O3 and PSN stands for Pb(Sc1/2Nb1/2)O3] relaxor ferroelecs.232 Novel nonstoichiometric mixed lead and Sn niobates with the pyrochlore structure were synthesised via a solid-state route. The materials were characterised by bulk chemical analysis, single-crystal and powder X-ray diﬀraction, 207Pb, 119Sn and 93Nb (single and triple quantum) solid-state NMR spectroscopy.233 207Pb, 45Sc and 93Nb nuclear-magnetic-resonance (NMR) spectra of partially ordered relaxor ferroelectric PbSc1/2Nb1/2O3 (PSN) were studied at 77– 420 K234 [PBun4]2[PbPh2Cl4] and [PPh4][PbPh3Cl2] were characterised by NMR (1H, 13 C, 31P and 207Pb), IR, MS and X-ray crystallography.235 In the solid state, heavier NMR-active nuclei such as 195Pt, 199Hg and 207Pb commonly exhibit chemical shifts that range well over 1000 ppm, depending upon the orientation of the mol. within the applied magnetic ﬁeld. Thus, acquiring NMR spectra of polycrystalline samples is often an experimental challenge because of these very broad powder patterns. In acquiring chemical shift powder patterns of these nuclei, the authors provide several examples that demonstrate that a considerable saving in time is realised by using the CPMG experiment as opposed to the standard 1-pulse or spin-echo experiment.236 A Pb(II) complex with three ligands, 4,4 0 -bipyridine (4,4 0 -bpy), nitrate and thiocyanate, was synthesised and characterised by CHN elemental analysis, IR-, 1H-, 13C- and 207 Pb NMR spectroscopy.237 A 2.8 kV/cm electric ﬁeld was applied parallel to the external magnetic ﬁeld along the [111] direction of a PMN single crystal and the 207 Pb NMR spectra were measured at 9.1 T.238 The coordination polymer Pb[B(Im)4](NO3)(xH2O), constructed by using Na tetrakis(imidazolyl)borate and Pb(NO3)2 solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturally occurring layered minerals, this compound can readily undergo anion exchange and reversible intercalation of solvent H2O in the solid state with retention of crystallinity. The authors observed changes in solvent intercalation by 207Pb solid state NMR (SSNMR) and TGA.239 2.15 Group15 (14,15 N,

31

P)

2.15.1 Nitrogen (14,15 N) (I = 1, 1/2). The measurement of amide nitrogen 14N quadrupolar coupling by two-dimensional 14N/13C correlation experiment is presented with a natural abundant polypeptide. Directly bonded 14N/13C pairs are correlated through J and residual dipolar coupling under magic-angle spinning using a HMQC-type pulse sequence. The 14N quadrupolar coupling is measured from the isotropic second-order quadrupolar shift obtained by comparing the 14N peak positions with the 15N chemical shifts.240 The high resolution oﬀered by magicangle spinning (MAS), when compared to the static condition in solid-state NMR of powders, was used to full advantage in a 14N MAS NMR study of some ammonium salts: CH3NH3Cl, (NH4)2(COO)2 H2O, Me3(C6H5CH2)NCl, Me3PhNI, [Bu4N]2Mo2O7, (NH4)2HPO4 and NH4H2PO4.241 Derivatives of 3-imidazoline 3-oxide were studied by 14N and 17O NMR methods. Regularities of the inﬂuence of substituents and of a hydrogen bond on chemical shifts were made apparent.242 13C, 14N, 15N, 17 O and 35Cl NMR parameters, including chemical shift tensors and quadrupolar tensors for 14N, 17O and 35Cl, are calculated for the crystalline forms of various amino acids under periodic boundary conditions and complemented by experiment where necessary.243 The electronic structures and mol. properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 were studied using various ab initio and density functional methods. Predictions for the vibrational frequencies, IR intensities, Raman activities and 14N, 15N, 77Se chemical shifts, as well as singlet excitation energies of Se2N2 and SeSN2, were made.244 GaN crystals doped with Mn ions were synthesised by the alkali metal ﬂux method. Mixtures of metals were premelted to form an alloy and the alloy was mixed with Na/K and heated to E8001 under E1400 psi N2 in an Al2O3 crucible. Up to 2 mol% Mn could be incorporated into the h-GaN lattice, and the products were characterised by solid state 71Ga, 69Ga, 14N NMR, magnetometry, Raman spectroscopy and powder X-ray Nucl. Magn. Reson., 2007, 36, 72–112 | 93 This journal is

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diﬀraction.245 Exploiting naturally abundant 14N and 31P nuclei by high-resolution MAS NMR (magic angle spinning NMR) provides a molecules view of the electrostatic potential present at the surface of biol. model membranes, the electrostatic charge distribution across the membrane interface and changes that occur upon peptide association. The spectral resolution in 31P and 14N MAS NMR spectra is suﬃcient to probe directly the negative charged phosphate and positive charged choline segment of the electrostatic PQO–CH2–CH2–N+(CH3)3 headgroup dipole of zwitterionic DMPC (dimyristoylphosphatidylcholine) in mixed-lipid systems.246 14 N magic-angle spinning NMR spectra were obtained and analysed for the nitrate ions of the two isomorphous room-temperature phases RbNO3(IV) and CsNO3(II).247 This review covers current trends in studies of membrane amphiphiles and membrane proteins using both fast tumbling bicelles and magnetically aligned bicelle media for both solution state and solid state NMR.248 The author’s results obtained from studies of the chemical micro-mechanisms of nitramines initiation from the point of view of organic chemistry were summarised. The relationships were presented and discussed between the characteristics of impact and electric spark sensitivities, detonation and thermal decomposition, on the one hand, and 15N NMR chemical shifts of N atoms of nitroamino groups, on the other.249 A review describes the recent progress in studies of RNA-metal systems. The metal ligands provides the chemical basis for mechanistic studies of metal complexes. Topics discussed include the hammerhead ribozyme and its metal ion-binding motif; analysis of titration experiments by 15N NMR spectroscopy; perturbations in 1H and 13C chemical shifts; interactions with other metal cations; comparisons with crystal structures; possible functions of a shared-type G–A pair in biological systems; sequence requirements for the binding of metal ions; and roles of the metal cation at the binding motif.250 Antimicrobial peptides are key components of innate immunity of all life forms. Understanding the structure activity relationship of these peptides is essential for developing them into novel therapeutics that substitutes traditional antibiotics. NMR spectroscopy can provide insights into membranetargeting antimicrobial peptides from a variety of angles.251 A review on the synthesis and structure of side-on-bound dinitrogen complexes of lanthanides, actinides and transition elements over the past 40 years is given. Hydrogenation and alkyne addition to side-on transition metal dinitrogen complexes yielded in sideon-coordinated (alkenyl)hydrazido species, cleavage of the N–N-bond gave nitridoand amido-bridged complexes. A compilation of N–N-bond lengths and 15N NMR chemical shifts, IR and Raman data for side-on metal dinitrogen complexes is presented.252 XPA, a 273 amino acid protein, is involved in the early stage of the nucleotide excision repair, by which a variety of DNA lesions are removed from the genome. NMR was used to analyze the structure of the central domain of XPA, which encompasses residues 98 to 219, and contains a zinc coordinating motif. Following chemical shift assignments of the backbone and side-chain 1H, 15N and 13 C nuclei, the tertiary structure was determined by multi-dimensional and multiresonance NMR methods.253 NMR spectroscopy is rapidly becoming an important technique for the study of membrane protein structure and dynamics. NMR experiments on large perdeuterated proteins typically exploit the favorable relaxation properties of backbone amide 15N–1H groups to obtain sequence-speciﬁc chemical shift assignments, structural restraints and a wide range of dynamics information.254 This contribution reviews applications of NMR spectroscopy in the study of the structure and the intra- and intermolecular interactions of purine derivatives. Purines represent a highly important class of heterocyclic compounds that are widely distributed in all living organisms, not only as constituents of nucleic acids, but also as signal molecules. In the following text, NMR methods suitable for studying the purine structure and their application to exploring samples at natural levels of the 13C and 15N isotopes are brieﬂy reviewed. As are shown, isotropic 13C and 15N chemical shifts, 1H–13C one- and three-bond J-coupling constants and 1 H–15N one- and two-bond couplings are the commonly used characteristic 94 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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parameters for NMR in the solution state.255 Diﬀerent symmetrical substituted and cyclic dialkydithiocarbamate (R = CH3, C2H5, C3H7, i-C3H7, C4H9, i-C4H9 and R2 = (CH2)5, (CH2)6, (CH2)4O) compounds, such as tetraalkylthiuram disulﬁdes, mononuclear nickel(II), binuclear zinc(II) and heteropolynuclear complexes and their adducts (both non-solvated and solvated forms) with planar and non-planar Ndonor org. bases, were prepared and studied by means of natural abundance 13C and 15 N CP/MAS NMR spectroscopy.256 2.15.2 Phosphorus (31P) (I = 1/2). Diﬀerent K salts and Zn(II) and Ni(II) O,O 0 dialkyldithiophosphate complexes were studied by solid-state 31P CP/MAS and static NMR and ab initio quantum mechanical calculations.257 Polycrystalline tetranuclear Cu4[S2P(O-i-C3H7)2]4, hexa-nuclear Cu6[S2P(OC2H5)2]6 and octa-nuclear Cu8[S2P(O-i-C4H9)2]6(S) complexes were synthesised and analysed by means of solid-state 31P CP/MAS and 65Cu static NMR spectroscopy.258 Glasses and melts in the system (NaPO3)(1x)(Al(PO3)3)x were studied with the aim of obtaining information about the structure on the next larger scale beyond the PO4 group. Magic angle spinning NMR was applied to the pure NaPO3 glass and Raman scattering to systems with x = 0.00, 0.03, 0.06, 0.15 and 0.60 in the temperature range T = 300–1100 K. Comparison of the 31P chemical shift between glass and crystalline forms revealed that polymerisation of the metaphosphate into tricyclophosphatelike (PO3)3(3-) rings is the dominant structure, ca. 80%, formed by the twofold vertex-joined PO4 groups in the glass.259 Coronary angiography is still the gold standard for the diagnosis of cardiac allograft vasculopathy (CAV) for which alternative non-invasive diagnostic approaches are currently investigated. In this study, the authors assessed whether 31P magnetic resonance chemical shift imaging can diagnose CAV by studying variations in cardiac high-energy phosphates in a population of adult heart transplant recipients.260 In the present study the authors applied proton-decoupled 31P magnetic resonance spectroscopic imaging (MRSI) to noninvasively assess liver metabolism in patients who had undergone a partial hepatectomy (PH). Proton-decoupled 31P chemical shift imaging was performed in 47 patients 2–28 days following major hepatectomy, and the results were compared with those from eight control subjects.261 The interactions of synthetic chalcocite surfaces with diethyldithiophosphate, potassium salt, K[S2P(OC2H5)2], are studied by means of 31P cross-polarisation/magic angle spinning (CP/MAS) NMR spectroscopy and scanning electron microscopy (SEM).262 Three new amine-templated zinc phosphates, [C4N2H14][Zn(HPO4)2] H2O, AU-I, [C4N2H14][Zn2(H(0.5)PO4)2 (H2PO4)], AU-II and [C4N2H14][Zn5(H2O)(PO4)4], AU-III, are prepared by hydrothermal synthesis using an organic amine, N,N 0 -dimethylethylendiamine CH3NHCH2CH2NHCH3, as structure-directing agent. The phase stability investigated by systematic hydrothermal synthesis is presented, and the materials are further characterised by 31P solid-state MAS NMR, for example, by determination of 31P chemical shift anisotropies for AU-III, while the thermal behaviour is investigated by thermogravimetry (TG).263 2.16 Group 16 (17O,

33

S,

77

Se,125Te)

2.16.1 Oxygen (17O) (I = 5/2). Sodium germanate glasses are well-studied materials in which, unlike silicates but analogous to borates, the major structural consequence of alkali addition is generally thought to involve a coordination no. increase of the network-forming Ge cations. However, the nature of this change, in particular quantifying fractions of nonbridging oxygens and of ﬁve- and/or sixcoordinated Ge, has remained unresolved. The authors present here high-resolution 17 O results, including triple-quantum MAS NMR (3QMAS), on a series of crystal model compounds that allow the deﬁnition of ranges of chemical shifts corresponding to oxygens bonded to various coordinations of Ge.264 Eﬀects of temperature and some aqueous solutions of electrolytes consisting of ions in natural water on the Nucl. Magn. Reson., 2007, 36, 72–112 | 95 This journal is

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chemical shifts of NMR of water (17O NMR) are measured.265 The natural abundance 17O NMR chemical shift data for 3,5-diarylisoxazoles (1a–k) and 3,5diarylisoxazolines (2a–j) in acetonitrile at 75 1C are reported.266 A phosphane sulfate relativistic DFT method (ZORA) was used to calculate the 183W and 17O NMR chemical shifts for large polyoxotungstates, including W6O192, CH3OTiW5O183, W5O18WIINO3, W10O324, a-d-g-XW12O40n, b-PW9O28Br63, P2W18O626, PW2O143 and W7O246, based on their optimised molecular structures.267 A relativistic DFT method (ZORA) is used to calculate the 183W and 17O NMR chemical shifts for the reduced polyoxotungstates W5O18WIINO3, g-SiW12O406, P2W18O628 and W10O326 with diﬀerent degrees of (de)localisation of the electrons introduced.268 17O NMR spectroscopy of oxo ligand of oxo metalloporphyrin can be considered as an excellent means to derive information about structure, electronic state and reactivity of the metal bound oxo ligand. To show the utility of 17O NMR spectroscopy of oxo ligand of oxo metalloporphyrin, 17O NMR spectra of oxo ligands of dioxo ruthenium(VI), oxo chromium(IV) and oxo titanium(IV) porphyrins are measured.269 The authors investigate the performance for nuclear magnetic constants calculations for a selective set of density functional methods (B3LYP, PBE0, BLYP, PBEPBE, OLYP and OPBE). The testing set includes the 13C, 15N, 17 O and 19F magnetic shieldings and chemical shifts of 23 molecules with 64 comparisons altogether.270 The 17O chemical shifts of substituted benzyl ethers and a set of organotin(IV) derivatives containing O,C,O-chelating ligands are studied.271 17O NMR spectra of a-diesters are measured at natural abundance in acetonitrile solutions.272 Derivatives of 3-imidazoline 3-oxide were studied by 14N and 17O NMR methods.273 A systematic solid-state 17O NMR study of a series of carboxylic compound, maleic acid, chloromaleic acid, KH maleate, KH chloromaleate, K2 chloromaleate and LiH phthalate MeOH, is reported.274 The solvent exchange between bulky TMU (1,1,3,3-tetramethylurea) molecules and the TMU molecules bound to metal cations (Mn(II), Fe(II), Ni(II), Cu(II) and Fe(III)) in neat TMU was studied by the oxygen-17 NMR line-broadening and chemical shift method.275 Two novel derivatives of TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triazadodecanedioic acid), TTDA-BOM and TTDA-N 0 -BOM, each having a benzyloxymethyl group, are synthesised. 17O NMR longitudinal and transverse relaxation rates and chemical shifts of aqueous solutions of their Gd(III) complexes were measured at variable temperature with a magnetic ﬁeld strength of 9.4 T.276 Water clusters of Na+, K+ and NH4+ ions with Cl and I counterions were studied using 17 O NMR spectroscopy.277 Among the synthesis of a series of ﬁve well-known 2triﬂuoroacetyl-1-methoxycycloalkenes derived from cyclopentanone and substituted cyclohexanones, this paper describes the synthesis of three new 2-triﬂuoroacetyl-1methoxycycloalkenes derived from cycloheptanone, cyclooctanone and cyclododecanone in 60–68% yield. Subsequently, the 17O NMR chemical shift analysis of the carbonyl and the methoxy groups for these cyclic molecules clearly showed the electron push-pull phenomenon and revealed large and irregular variations of 17O NMR chemical shifts with the ring size.278 The complex formation of uranium(VI) with four nucleotides, adenosine- (AMP), guanosine- (GMP), uridine- (UMP) and cytidine-monophosphate (CMP), was studied in the alkali pH range (8.5–12) by 1H, 31 P, 13C and 17O NMR spectroscopy, providing spectral integral, chemical shift, homo—and heteronuclear coupling and diﬀusion coeﬃcient data.279 1H, 19F, 13C, 15 N and 17O NMR chemical shifts and 1H–1H, 1H–19F, 1H–13C, 19F–13C and 19 F–15N coupling constants are reported for 2-(triﬂuoromethyl)-2-oxazoline.280 Solution 17O NMR spectroscopy was used for structure elucidation of siloxane copolymers with the natural abundance of 17O, i.e. without any enrichment prior to spectroscopy.281 Recently available ultrahigh magnetic ﬁelds oﬀer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of secondorder quadrupole interactions. Here, the authors present a new approach for understanding the function and energetics of ion solvation in channels using solid96 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A.282 13C, 14N, 15 N, 17O and 35Cl NMR parameters, including chemical shift tensors and quadrupolar tensors for 14N,17O and 35Cl, are calculated for the crystal forms of various amino acids under periodic boundary conditions and complemented by experiment where necessary.283 A variety of computational tools were used to study the chemical properties of point defects in the crystalline phase of ZrSiO4, and their eﬀect in its lattice parameters. Our calculations also show that vol. swelling in crystal ZrSiO4 would produce a considerable displacement of the 17O and 91Zr chemical shifts towards higher values, whereas the 29Si spectra would be largely independent of the defect-induced swelling.284 The temperature dependence of 17O and 25Mg NMR chemical shifts in solid MgO were calculated using a 1st-principles approach.285 The structure of poly di-Et siloxane (PDES) was characterised using solid-state NMR of 17 O.286 The salvation shell structure of Y3+ and the dynamics of the hydrated ion in an aqueous solution of 0.8 M YCl3 are studied in two conditions with and without an excess proton by using ﬁrst principles molecular dynamics method. A detailed analysis relying upon localised orbitals reveals that the complexation of water molecules with yttrium cation leads to a substantial amt. of charge redistribution particularly on the oxygen atoms, giving rise to the chemical shifts of E20 ppm in 17 O NMR relative to the computed nuclear shieldings of the bulk water.287 The 17O NMR spectrum of CaAl2Si2O8 glass shows two types of O sites that are not present in the crystal material. One of these, with 17O NMR parameters CQ = 2.3 MHz and d = +20 ppm, was assigned to a ‘‘tricluster’’ O, a local geometry in which the O is coordinated to three tetrahedrally coordinated atoms, either Al or Si.288 The N 0 -monoamide derivatives of TTDA (3,6,10-tri(carboxymethyl)-3,6,10triazadodecanedioic acid), N 0 -methylamide (TTDA-MA), N 0 -benzylamide (TTDABA) and N 0 -2-methoxybenzylamide (TTDA-MOBA), were synthesised. The 17O NMR chemical shift of H2O induced by [Dy(TTDA-MA)(H2O)] at pH 6.80 showed 0.9 inner-sphere H2O molecules.289 2.16.2 review.

Sulfur (33S) (I = 3/3). No reference was founded during the period of this

2.16.3 Selenium (77Se) (I = 1/2). 1,3-Bis(ferrocenylchalcogeno)propanes (FcE (CH2)3E 0 Fc, E and E 0 = Se and Te) and 1,2-bis(ferrocenylseleno)ethane (FcSe(CH2)2SeFc) were prepared, characterised and included in a spectroscopic and electrochemical study of a series of compounds containing two ferrocenes linked by a chalcogen-containing bridge. 77Se and 125Te NMR spectroscopic measurements reveal that the 77Se chemical shift of Fc2Se2 is anomalously high, which correlates with the long wavelength of its lowest energy electronic absorption.290 The orientational eﬀect of p-YC6H4 (Ar) on d(Se) is elucidated for ArSeR, based on experimental and theoretical investigations.291 The oxidation products of selenomethionine (SeMet) are studied via experimental 77Se NMR and theoretical 77 Se chemical shifts.292 The theoretical chemical shifts of a large series of selenium compounds are calculated using GIAO-MP2 and -DFT methods in several basis sets.293 The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 are studied using various ab initio and density functional methods. Predictions for the vibrational frequencies, IR intensities, Raman activities and 14N, 15N, 77Se chemical shifts, as well as singlet excitation energies of Se2N2 and SeSN2, were made.294 Weak nonbonded interaction between a divalent selenium and an oxygen atom (i.e., Se O interaction) frequently plays important roles in chemical and biological functions of selenium compounds. To establish that 77Se NMR is an easy experimental probe to diagnose the strength of an Se O interaction, 3 series of 2-substituted benzeneselenenyl derivatives, which have an intramolecular Se O interaction in solution, were employed. By comparing the 77Se NMR chemical shifts (dSe) with those observed for other series of Nucl. Magn. Reson., 2007, 36, 72–112 | 97 This journal is

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selenium compounds, which have an intramolecular Se Y (Y = N, O, F, Cl, or Br) interaction, approximately linear correlation was found between the dSe values and the strengths of the nonbonded Se Y interactions evaluated by natural bond orbital analysis at the B3LYP level.295 Three mixed ligand complexes of Au(I) with phosphines and selenones, [Et3PAu(Se:Co)]Br [Se:C o = imidazolidine-2-selenone (ImSe), N-methylimidazolidine-2-selenone (MeIMSe), 1,3-diazinane-2-selenone (DiazSe)] as analogs of auranoﬁn (Et3PAuSR) were prepared and characterised by elemental anal., IR and NMR methods. Large 77Se NMR chemical shifts (55 ppm) upon complexation in the solid state for [Et3PAuDiazSe]Br compared to [Et3PAuImSe]Br (10 ppm) indicates the former to be more stable and the Au–Se bond to be stronger than in the latter complex.296 The ability of MP2, B3PW91 and PBE0 methods to produce reliable predictions in structural and spectroscopic properties of small Se-halogen molecules and cations was demonstrated by using 6-311G(d) and cc-pVTZ basis sets. The calculated isotropic shielding tensors can be used in the spectroscopic assignment of the 77Se chemical shifts of novel Se-halogen molecules and cations.297 Phosphinoselenoic chlorides bearing two diﬀerent organic substituents at phosphorus were prepared by partial alkylation or arylation of phenyldichlorophosphine in the presence of elemental selenium; phosphinoselenoic esters, thio- and selenoesters were also prepared. Linear correlations were observed between the experimental 77Se NMR chemical shifts or the coupling constants of P–Se bonds in the esters and the calculated P–Se bond lengths of the model compounds.298 2.16.4 Tellurium (125Te) (I = 1/2). 1,3-Bis(ferrocenylchalcogeno)propanes (FcE(CH2)3E 0 Fc, E and E 0 = Se and Te) and 1,2-bis(ferrocenylseleno)ethane (FcSe(CH2)2SeFc) were prepared, characterised and included in a spectroscopic and electrochemical study of a series of compounds containing two ferrocenes linked by a chalcogen-containing bridge. Cyclic and diﬀerential pulse voltammetry show that there is electronic communication between the two ferrocene units when the bridge is short (as in Fc2E), but that the interaction rapidly becomes weaker with increasing Fe Fe distance, and is undetectable for the ethane and propane derivatives. 77Se and 125Te NMR spectroscopic measurements reveal that the 77Se chemical shift of Fc2Se2 is anomalously high, which correlates with the long wavelength of its lowest energy electronic absorption.299 The quasirelativistic (QR) generalised UHF method for the magnetic shielding constant [R. Fukuda, M. Hada and H. Nakatsuji, J. Chem. Phys., 2003, 118, 1015; R. Fukuda, M. Hada and H. Nakatsuji, J. Chem. Phys., 2003, 118, 1027] was extended to include the electron correlation eﬀect in the level of the 2nd-order Moller-Plesset perturbation theory (MP2). The authors implemented the energy gradient and ﬁnite-perturbation methods to calculate the magnetic shielding constant at the QR MP2 level and applied to the magnetic shielding constants and the NMR chemical shifts of 125Te nucleus in various tellurium compounds.300 A series of N-arylimines of 2-telluro-2cyclohexene-1-carboxaldehydes were prepared; their crystal structures indicate dative hypervalent-type bonding interactions between tellurium and imine nitrogen. 2-Chloro-1-cyclohexenecarboxaldehyde was coupled with MeTeLi; after bromination of the tellurium atom and reaction with ArNH2, [2-(XTe)-1-cyclohexenylmethylene]arylamines (X = OAc, Br, F; aryl = 2,6-Me2C6H3, 4-MeC6H4) were prepared. Aryltelluro compound (X = 4-EtOC6H4, Ar = 4-MeC6H4) was also prepared. Crystal structures of these compounds were determined, and Te–N distances indicate strong dative interactions for compounds bearing electronegative substituents at tellurium (Br, F, OAc). The 125Te NMR chemical shifts of these compounds span the wide range of 734.3–1622.4 ppm.301 2.17 Group 17 (19F,

35,37

Cl)

2.17.1 Fluorine ( F) (I = 1/2). 19F NMR spectra of two neutral, organic-soluble helical peptide octamers, each labeled at its N terminus with either 19

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4-ﬂuorobenzamide or 4-triﬂuoromethylbenzamide, in solvents with widely varying dielectric constants were observed.302 1H-decoupled 19F NMR was used to monitor the highly regioselective oxidation of a ﬂuorine-tagged thia-fatty acid derivatives by castor stearoyl-ACP D9 desaturase.303 Human manganese superoxide dismutase (MnSOD) is a homotetramer of 22 kDa subunits, a dimer of dimers containing dimeric and tetrameric interfaces. The authors investigated conformational mobility at these interfaces by measuring amide hydrogen/deuterium (H/D) exchange kinetics and 19F NMR spectra, both being excellent methods for analyzing local environments.304 19F NMR chemical shifts are calculated in order to study the F-environment in double four ring (D4R) containing Si/Ge-zeolites.305 A series of 19 psubstituted aromatic triﬂuorovinyl ether compounds were prepared from versatile intermediatep-Br-C6H4-O-CF:CF2 and underwent thermal radical mediated cyclodimerisation to new difunctional compounds containing the 1,2-disubstituted perﬂuorocyclobutyl (PFCB) linkage. 19F NMR spectra conﬁrmed that p-substitution aﬀects the triﬂuorovinyl ether group chemical shifts.306 The authors investigate the performance for nuclear magnetic constant calculations for a selective set of density functional methods (B3LYP, PBE0, BLYP, PBEPBE, OLYP and OPBE). The testing set includes the 13C, 15N, 17O and 19F magnetic shieldings and chemical shifts of 23 molecules with 64 comparisons altogether.307 The authors report the eﬀective 19F NMR chemical shift of 3-ﬂuorobenzoic acid as in situ probe of the acidity of extensively frozen electrolyte solutions.308 The conformational free energy (A value) of the triﬂuoromethyl group was determined by variable temperature 19F NMR studies of triﬂuoromethylcyclohexanes bearing a substituent at the 4 position.309 For the ﬁrst time, a small amount of sevoﬂurane ((CF3)2CHOCH2F) in carbon dioxide and xenon as the gaseous solvents was studied using 19F and 1H NMR spectra.310 For the ﬁrst time, theoretical evidence that conﬁrms the importance of the Berry pseudorotation process in the interpretation of the 19F NMR spectrum of phosphorus pentaﬂuoride (PF5) is presented.311 Gene therapy has emerged as a promising strategy for treatment of various diseases. The authors previously demonstrated the ability to detect b-galactosidase (b-gal) activity on the basis of 19F NMR chemical shift associated with release of ﬂuorophenyl aglycons from galactopyranoside conjugates. Use of ﬂuoropyridoxol as the aglycon provides a potential less toxic alternative and the authors now report the design, synthesis and structural analysis of a series of novel polyglycosylated ﬂuorinated vitamin B6 derivatives as 19F NMR-sensitive aglycons for detection of lacZ gene expression.312 19 F NMR chemical shifts and transverse relaxation times T2 were measured as a function of time after quick stopped-ﬂow dilution of aqueous solutions of sodium perﬂuorooctanoate (NaPFO) with water.313 THF solutions of the cationic chiral 1,3diphenylallyl bidentate phosphine complexes lsqb;Pd(Z3-PhCHCHCHPh)(Duphos)](CF3SO3), Duphos = 1,2-Bis-[(2R,5R)-2,5-dimethylphospholanoenzene], 2 and [Pd(Z3-PhCHCHCHPh)(P,S)]BF4, 4, P,S = lsqb;8-(o-(diphenylphosphino)benzyl)thiomethyl]-(7,7 0 -dimethyl)-exo-norborneol, were studied via pulsed gradient spin-echo (PGSE) diﬀusion, 1H, 19F HOESY and a variety of other multi-dimensional NMR methods.314 b-CaAlF5 was synthesised by solid-state reaction. The precise structure was reﬁned from X-ray powder diﬀraction data in the monoclinic space group P21/c with a 5.3361, b 9.8298, c 7.3271 A˚ and b 109.911(Z = 4). Crystallographic data and atomic coordinates are given. 19F and 27Al solid state NMR spectra were recorded using MAS and SATRAS techniques.315 The authors report the design, synthesis and evaluation of novel enhanced reporter molecules, which reveal lacZ gene expression: triﬂuoromethylated aryl b-D-galactopyranosides. P-Triﬂuoromethyl-o-nitrophenyl b-D-galactopyranoside (PCF3ONPG) was found to exhibit valuable properties including a single 19F NMR signal, stability in aqueous solution and with wild type cells, but a chemical shift response to enzyme cleavage (Dd = 1.14 ppm) in breast cancer cells transfected to stably express lacZ.316 Intermediates formed in halogen addition (X = Br, Cl, F) to alkynes (ethyne, propyne, 2-butyne, triﬂuoromethylethyne, trimethylsilylethyne and Nucl. Magn. Reson., 2007, 36, 72–112 | 99 This journal is

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1-trimethylsilylpropyne) were studied computationally by MP2 at the MP2/ 6-311++G(3df,3pd) level and/or by DFT at the B3LYP/6-31+G(d) level. Structure optimisation and frequency calculations were performed to identify the min. and to obtain their relative energies. PCM calculations (with H2O, CH2Cl2 and CCl4 as model solvents) were employed to examine solvation eﬀects on the relative stabilities in the resulting bridged halonium, b-halovinyl, or a-halovinyl cations. GIAO-MP2 and GIAO-DFT calculations were employed to compute NMR chemical shifts (13C, 19F and 29Si as appropriate).317 1H, 19F, 13C, 15N and 17O NMR chemical shifts and 1H–1H, 1H–19F, 1H–13C, 19F–13C and 19F–15N coupling constants are reported for 2-(triﬂuoromethyl)-2-oxazoline.318 The long-range coupling constants (JFH) of 1-methylpyrazoles and the chemical shifts of triﬂuoromethyl groups in the 19F NMR spectra can be used for the determination of regio-isomeric structures of mono(triﬂuoromethyl)-substituted pyrazoles.319 The authors present a facile 19F NMR spectroscopic approach for the characterisation of bistable RNA.320 Monoﬂuorinated polycyclic aromatic hydrocarbons (F-PAHs) have attracted much attention in analytical, environmental, toxicological and mechanistic studies because of their physico-chemical properties, which are closely similar to those of the parent PAHs. Because of this, full NMR characterisation has become of interest. Complete 1 H, 13C, 19F NMR chemical shifts, and also 1J(H,C), nJ(C,F), nJ(H,F) and nJ(H,H) coupling constants, were assigned for the F-PAHs 1-ﬂuoronaphthalene, 2-ﬂuoroﬂuorene, 5-ﬂuoroacenaphthylene, 2-ﬂuorophenanthrene, 3-ﬂuorophenanthrene, 3-ﬂuoroﬂuoranthene, 1-ﬂuoropyrene, 1-ﬂuorochrysene, 2-ﬂuorochrysene, 3-ﬂuorochrysene and 9-ﬂuorobenzo[k]ﬂuoranthene.321 The authors present a simple model for predicting the principal site for nucleophilic substitution in aromatic perﬂuorocarbons. Model is based on the relative stabilities of the Meisenheimer complexes as calculated using density functional theory with a modest basis set. (Hartree-Fock theory will do just as well.) Predictions from model agree with experimental observations for 16 aromatic perﬂuorocarbons, and together with additional NMR calculations, lead us to conclude that the earlier prediction that perﬂuoroanthracene undergoes nucleophilic substitution in the 2-position is incorrect, and is based on a misinterpretation of the experimental 19F NMR spectrum.322 The insulin hexamer is an allosteric protein widely used in formulations for the treatment of diabetes. The hexamer exhibits positive and negative cooperativity and apparent half-site binding activity, reﬂecting the interconversion of three allosteric states, designated as T6, T3R3 and R6. The authors exploit the high sensitivity of 19F NMR chemical shifts and ﬂuorinated carboxylates to reveal subtle diﬀerences in the anion-binding sites of T3R3 and R6.323 A computational study shows that Ge is pentacoordinated in the double four rings (D4R) of Si/Ge AST zeolites; the calculated chemical shifts of F-D4R containing 8Si, 7Si1Ge and 8Ge reproduce the trends of 19F NMR experiments.324 Seventeen N-(mono-, di-, tri-, tetra- and penta-ﬂuorophenyl)-N 0 -(3-nitrophenyl)ureas were prepared and characterised. Complete assignment of their 1H, 13C and 19F NMR data was undertaken and the correlation of the chemical shifts of the ureido protons with ﬁeld-inductive and mesomeric electronic substituent parameters was studied using the Swain-Luptonmodel.325 A series of sterically hindered o-hydroxy Schiﬀ bases derived from o-hydroxyaceto- and benzophenones with very short intramolecular hydrogen bonds were described. Structures, 1H, 19F, 13C chemical shifts and deuterium isotope eﬀects on 13C chemical shifts were calculated by ab initio methods.326 The stability constants for the diaza-18-crown-6 ethers (2–6) and alkali metal cations (Na+, K+, Rb+ and Cs+) were determined using potentiometry in 95% methanol. For each metal ion the stability constants of the partially-ﬂuorinated ligands 3–6 were larger than that of the non-ﬂuorinated ligand 2, which might reﬂect an interaction between ﬂuorine atoms and alkali metal cations. The stability constant of the ligand 4 was larger than that of the ligand 5 for each metal cation tested. This ﬁnding was also supported by the results of cation-induced chemical shifts in 1 H-, 19F-NMR.327 19F NMR isotropic chemical shift calculations were performed in 100 | Nucl. Magn. Reson., 2007, 36, 72–112 This journal is

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crystalloid compounds using the GIAO method with the B3LYP hybrid functional at DFT level.328 The inﬂuence of water on the NMR and IR spectra of bis((perﬂuoroalkyl)sulfonyl)imides was investigated.329 The higher order high-resolution 31 P and 19F NMR spectra of hexaﬂuorocyclotriphosphazene (F2PN)3 were measured at 183 K and interpreted using subspectral analysis and iterative ﬁtting computation.330 The 19F NMR nuclear shieldings of ﬂuoride ligands in uranium complexes UFnCl6n (n = 1–6) were studied quantum chemistry, using diﬀerent exchangecorrelation functionals and a relativistic small-core pseudopotential on uranium.331 Relativistic density functional theory (DFT) was applied to the calculation of the 19F and 235U NMR chemical shifts of uranium(VI) chloride ﬂuorides UF6nCln.332 Ten crosslinked polystyrene-supported, protected chiral amines featuring both a spacer, comprising from 5 to 15 atoms, and a ﬂuorinated linker were successfully prepared. The development of the monitoring technique by gel-phase 19F NMR spectrometry on cross-linked polystyrene derivatives proved to be of high value in four steps of the process, as shown by the comparison of data gathered from both a classic NMR spectrometer and elemental analysis.333 A series of thioanilides and corresponding anilides, some of which contain ﬂuorinated Ph rings, were synthesised as model compounds. They all contain rather strong intramolecular hydrogen bonds, the strength of which varies. Deuterium isotope eﬀects on 19F and 13C chemical shifts due to deuteration at the NH proton show interesting new long-range isotope eﬀects on chemical shifts that may be related to the existence of an intramolecular hydrogen bond and to transmission of the isotope eﬀect due to an electrical ﬁeld eﬀect.334 2.17.2 Chlorine (35,37Cl) (I = 3/2,3/2). 1H, 23Na, 35Cl, 79Br and 81Br NMR chemical shifts and signal half widths were measured in aqueous electrolyte mixtures [tetrahydrofuran/H2O/NaCl and 3-methylpyridine (3MP)/H2O/NaBr] at diﬀerent mass fractions of salt (X) in the one-phase region, close to their lower critical soluble points (TCL).335 13C, 14N, 15N, 17O and 35Cl NMR parameters, including chemical shift tensors and quadrupolar tensors for 14N, 17O and 35Cl, are calculated for the crystal forms of various amino acids under periodic boundary conditions and complemented by experiment where necessary.336 The 35Cl NMR chemical shift and line width and the 1H chemical shifts of cetylpyridinium chloride, CPyCl, change abruptly at the critical micelle concentration, indicating conversion of monomeric surfactant into micelles within a very small range of concentration.337 The results of a detailed systematic chlorine solid-state NMR study of several hydrochloride salts of amino acids implicated in chloride ion transport channel selectivity are reported. 35 Cl and 37Cl NMR spectra were obtained for stationary and/or magic-angle spinning powder samples of the following compounds on 500 and/or 900 MHz spectrometers: DL-arginine HCl monohydrate, L-lysine HCl, L-serine HCl, L-glutamic acid HCl, L-proline HCl, L-isoleucine HCl, L-valine HCl, L-phenylalanine HCl and glycine HCl.338 2.18 Group 18 (3He,

83

Kr,

129

Xe)

2.18.1 Helium ( He) (I = 1/2). NMR spectra of 3He introduced in Linde-type A zeolites were traced, which show that chemical shifts depend on the cations incorporated in the micropore. The chemical shift reﬂects the interaction with cations, the magnitude of which depends on the eﬀective channel dimensions. 3He NMR can probe the smaller pores with much shorter periods than the conventional 129 Xe NMR.339 The chemical shift of tetramethylsilane (TMS) is usually taken to be zero. However, it does vary slightly with temperature, having obvious implications for studies of temperature eﬀects on chemical shifts. The authors measure the variation in the chemical shift of TMS with temperature in three solvents, CDCl3, CD3OD and DMSO-d6, relative to the resonant frequency of 3He gas, which can be reasonably assumed to be t temperature independent. Data are included for 3He 3

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resonance frequencies at 110 to +1801, along with new measurements of volume magnetic susceptibilities of the three solvents and estimates of their temperature dependence.340

2.18.2 Krypton (83Kr) (I = 9/2). A w