Nuclear Magnetic Resonance Spectroscopy

BY B. E. MANN

1 Introduction

Following the criteria established in earlier volumes, only books and reviews directly relevant to this chapter are included, and the reader who requires a complete list is referred to the Specialist Periodical Reports 'Nuclear Magnetic Resonance', where a complete list of books and reviews is given. Reviews which are of direct relevance to a section of this Report are included in the beginning of that section rather than here. Papers where only 1H, 2H, 13C, 19F, and/or 31P NMR spectroscopy is used are only included when they make a non-routine contribution, but complete coverage of relevant papers is still attemptedwhere nuclei other than these are involved. In view of the greater restrictions on space, and the ever growing number of publications, many more papers in marginal areas have been omitted. This is especially the case in the sections on solid-state NMR spectroscopy, silicon and phosphorus.

Several reviews have been published which are relevant to this review:- 'Applications of NMR in solution inorganic chemistry of main elements', 'NMR spectroscopy of metal nuclei in solution', 'Nuclear magnetic resonance spectroscopy: A review of neuropsychiatric applications', which contains 7Li and 23N NMR data, 'NMR spectroscopy of transition metals', 'NMR of transition metal compounds', 'Two-dimensional 13C, heteroelement correlation spectroscopy', which contains 2H, 6Li, 11B, 15N, 19F, 29Si, 31P, 77Se 119Sn, 125Te 195Pt 199Hg, and 207Pb, Transition-metal NMR spectroscopy, Part XXVI. Spin-lattice relaxation times of transition metal nuclei from inverse detection experiments', 'Chemistry of vanadium and molybdenum complexes - some results and future prospects', 'Application of NMR to studies of ion dynamics in condensed matters', 'Multinuclear NMR in the chemistry of heteroatom-containing organic compounds', which contains N, O, V, Se, and 119Sn, 'In situ NMR', about adsorbates on metals, 'Characterisation of diastereomers by 31P{1H} NMR spectroscopy', is about chiral transition metal catalysts, and 'Applications of 31P shift and 31P 31P-31P coupling data in the chemistry of organometallics containing two or more phosphorus atoms'.

A number of papers have been published which are too broadly based to fit into a later section and are included here. Chemical shift derivatives of HSi(O)-X substituted first row hydrides have been calculated using the gauge invariant AO perturbed Hartree-Fock approach. An ab initio study of the chemical bond and the 129Xe NMR chemical bond has been carried out and the 129Xe NMR chemical shifts in M+ — Xe compounds, M = Li, Na, K, Cu, Ag, reported. 19F NMR spectra of a series of halogenated porphyrins have been used to create a spectral library of different types of fluorine splitting patterns for (C6F5) 4-porphyrins complexed with diamagnetic and paramagnetic metal ions. Metal ion complexation by the phosphoryl and carbonyl groups has been probed by 17O NMR spectroscopy. A database of NMR spectra of several transition metal elements from Group 3 through to Group 7 has been developed. Ligand 13C NMR chemical shifts in transition metal complexes have been calculated using ab initio effective-core potentials and density functional theory. An ab initio ECP/DFT study of scalar relativistic effects on 17O NMR chemical shifts in transition metal oxo complexes has been published. The determination of T1 of transition metal nuclei from inverse detection experiments has been described and applied to 57Fe in [η 5-C5H5)-Fe(CO)(PPh3)(COMe)], 103Rh in [(η5- C5Me5)RhCl2(PPh3)] and Os in 187Os in [η6-1,4-PriC6 Me)-OsCl(H)(PMe3)]. A new apparatus for the convenient measurement of NMR spectra in high-pressure liquids has been described and applied to 1H, 129Xe, and 19F studies of supercritical fluids, near-critical liquids, and high-pressure organometallic reactions. A 1H, 2H, 17O, 23Na, and 35Cl NMR study of RF losses in NaCl/D2O solutions has been reported. The theory of T1-1 and T2-1 NMRD profiles of solutions of magnetic nanoparticles has been developed. G1AO-MBPT(3) and GIAO-SDQ-MBPT(4) calculations of nuclear magnetic shielding constants have been applied to HF, H2O, NH3, CH4, CO, N2, HCN, and F2.

2 Stereochemistry

This section is subdivided into eleven parts which contain NMR information about Groups 1 and 2 and transition-metal complexes presented by Groups according to the Periodic Table. Within each Group, classification is by ligand type.

Complexes of Groups 1 and 2. — A review has appeared entitled 'NMR of organolithium compounds: general aspects and application of two-dimensional heteronuclear Overhauser effect spectroscopy (HOESY)', and contains 6Li and 133Cs NMR spectroscopy.

The use of nuclear spin polarised alkali metal beams in specific nuclear and surface physics experiments has been described and applied to the determination of the tensor part of the polarisability of 23Na, the spin lattice relaxation of 7Li on metal surfaces, and the determination of the sign of the quadrupole moment of 8Li. Ab initio MO calculations of 1J(13C1H) and 1J(13C7Li) in methyllithium and tert-butyllithium have been reported. Chelation effects in chiral organolithium reagents have been investigated by 7Li NMR spectroscopy. Homonuclear correlation experiments with quadrupolar nuclei have been applied to 7Li, 7Li COSY experiments for an organolithium compound. 1H, 1H-NOESY and 6Li,1H-HOESY studies of mixtures of a chiral lithium amide and n-butyllithium have been reported. Combined 13C,6Li and 1H, 7Li HOESY measurements have been applied to locating the position of lithium in 13C labelled benzyllithium. Contact ion pairing in PhSCHPhLi has been studied using J(13 C6Li) and 1H,6Li-HOESY. 1J(13C7Li) has been observed in allenyl lithium." An ah initio study of J(13C, 6,7Li) for [CHCl2Li], [CHCl2Li] 2, and [CCl3Li], has been reported. 1H and 13C NMR spectroscopy has been used to study the structure of sulfur stabilised lithiated allylic carbanions. The 13C NMR spectrum of C60Li in D2O gives a sharp peak at δ 171.44. Ab initio MO calculations have been used to calculate 1J(29Si7Li) in [H3SiLi] and [Me3SiLi], with solvent molecules coordinated. NMR data have also been reported for [{2,6-(Me2 NCH2)2-3,5-Me2 C6HCH2}2Li4Bun2],(6Li), [LiCPrn=CHPrn, (7Li), [LiC(OEt)=CH2]4, (6Li), (1), (M = Li, Na; 6Li, 23Na, 29Si), [{2,4,6-[(Me3Si)2CH]3 C6H2BH3}Li(THF)3 (11B), (2), (7Li), [(RO)3-nPhSiLi], (29Si), [(ButO)SiPh2Li], (29Si), [K{C(SiMe3-(Si Me2Ph))2]-, (29Si), and [MC (SiMe3)3], (M =...