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, 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 attempted where 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.

One book has been published which is relevant to this review:- 'NMR Techniques in Catalysis'. Several relevant reviews have been published, including 'Bipolarons and the temperature dependence of exchange in metal trihydrides', 'Lithium, cell membranes and ion transport processes', 'Small molecule analogues of phospholipid-metal ion binding sites: potentiometric and spectroscopic studies of Mg(II) and Ca(II) complexes of cyclohexane-1,2,4-triol trisphosphates', 'Electronic mechanisms of metal chemical shifts from ab initio theory', '(59Co, 195Pt) NMR of transition metals in clusters', 'New developments in structure characterization of organometallic complexes by nuclear magnetic resonance methods', 'NMR at elevated gas pressures and its application to homogeneous catalysis', 'Metal and organometallic phosphites and phosphonates', 'Multinuclear NMR (11B, 17O, 29Si, 51V, 17Ga, 77Se, 93Nb, 95Mo, 125Te, 183W, 195Pt) of polyoxometalates', 'Synthetic Haem-Dioxygen Complexes', (includes 17O), 17O NMR studies of oxygenated haemoproteins and synthetic model compounds', 'Multidimensional nuclear magnetic resonance methods to probe metal environments in proteins', '17O NMR studies of haemoproteins and synthetic model compounds in the solution and solid states', 'Aqueous aluminates, silicates, and aluminosilicates', (includes 27Al and 29Si), 'NMR at elevated gas pressures and its application to homogeneous catalysis', (includes 13C and 31P), 'NMR studies of molecular diffusion', 129Xe NMR in polymers', 'NMR of noble gases dissolved in isotropic and anisotropic liquids', and 'Electrophoretic NMR'. Conventions for the reporting of nuclear magnetic shielding (or shift) tensors have been suggested.

A number of papers have been published which are too broadly based to fit into a later section and are included here. Ab initio calculations have been applied to isotope effects in IR and NMR spectroscopy of hydrogen-bonded systems. A spin Hamiltonian suitable for quantum mechanical exchange has been developed. A study of Group 14 organometallic compounds has been carried out using 17O NMR spectroscopy. The GIAO method has been applied to calculate the individual tensor components of the magnetic shielding of 1H, 13C, 15N, 19F, 29Si, and 33S. NMR data have also been reported for [{HB(3a,7a-benzo-1,2,3-1H-triazol-1-yl)3)2M], (M = Mn, Fe, Co, Ni, Cu, Zn, Cd, Sn, Pb, VO; 13C), [{HB(3Me-pz)3}2M], (M = Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb; 13C), and [M{L-(-)-2,3,5,6-tetrahydro-6-phenylimidazo[2,1-b]thiazole}2Cl2], (M = Co, Ni, Cu, Zn; 14C).

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. — Reviews have appeared entitled 'Alkali metal nuclear magnetic resonance', (includes 6Li, 7Li, 23Na, 39K, 41K, 85Rb, 87Rb, and 133Cs), 'Are polar organometallic compounds 'carbanions'? The gegenion effects on structure and energies of alkali-metal compounds', (includes 6Li and 13C), 'Do crown ethers really include metal ions?', (includes NMR of Na+-(12-crown-4)), 'NMR imaging and localized spectroscopy of lithium', (includes 7Li), and 43Ca nuclear magnetic resonance'.

The sign of the quadrupole moment of 8Li has been determined. The 3He, 6Li, and 7Li NMR chemical shifts of endohedral fullerene compounds have been calculated using ab initio calculations. 7Li and 13C NMR spectroscopy has been used to study ion- pair structures of pyridine-butyllithium adducts. The aggregation behaviour of butyllithium, phenyllithium, and Li(NPri2) in (MeO)2CH2 and (EtO)2CH2 has been studied using J(13C6Li) and J(15N6Li). The NMR spectrum of vinyl-lithium has been calculated using ab initio methods. NMR data have also been reported for [(C4H8O)2Li(μ-H)2AlH{C(SiMe2Ph)3}]2, (7Li, 13C, 27Al, 29Si), [PhS(=NMe)(=O)CH2Li], (13C), (1), (7Li, 13C, 29Si), [Li{C(PMe2)2(SiMe2Ph)}]3, (13C), [Li(2-C5H4NCH=CHC5H4N-2)], (7Li, 13C), α-lithiomethoxyallene, (6Li, 13C), [M(μ-N=CButPh)3Li.THF], (M = Sn, Pb; 13C), [1,2,4,6-(Me3Si)4C6H2] Li(THF)]2, (7Li), [(η5-C5H5)2Li]-, (13C), [(η5-C5H4)2SLi2], (13C), (2), (7Li, 11B, 13C), (3), (13C), (4), (11B, 13C), (5), (1H{6Li} HOESY, 13C), (6), (7Li, 13C), [Na(THF)6][Li((2- NC5H4)2CH2}], (7Li, 13C, 23Na), [LiSiAr2SiAr2SiAr2Li], (Ar = 2-Me2NCH2C6H4; 7Li, 13C, 29Si), [Na(tmen)2(OEt2)][Na(C(SiMe)3}2], (13C, 29Si), [PhCH2M(PMDETA)]n (M = K, Rb; 13C), and [(PhMe2Si)3CK], (13C).

The solution structures of LiSePh and LiPPh2 have been studied by 7Li, 13C, 31P and 77Se NMR spectroscopy. 1J(Se6Li) = 18 Hz was observed for LiSePh. NMR data have also been reported for Li/Na-NH2CH2CH2NH2, (7Li, 23Na), [LiN(SiMe3)2], (6Li, 13C, 15N), [PhHCCN-(Li(TMEDA)}2N(SiMe3)2], (6Li; 13C; 15N), [LiN(CMe2CH2)CH2], (6Li, 13C, 15N), [M1{N-(CH2CH2OH)3}]+, [M2{N(CH2CH2OH)3}2]2 +, (M1 = Li, Na; M2 = Sr, Ba; 7Li, 13C, 23Na), [Li(PMDETA)2][Pt(CH2CH2CH2CH)2], (13C), [Li{CH6(CHNMeCH2CH2NMe2)- 2}]2, (7Li, 13C), [{MeN(CH2CHNMe2)2Li}2Cl] [HC{SiMe2N(C6H4Me-4)}3Sn], (13C, 29Si), [(Me3Si)2N-N(SiMe3)Li], (13C), [{(Me3Si)2N2Li2} {(Me3Si)2N2Li2}]2, (13C, 15n, 29Si), [Li(tetra-p-tolyl-porphyrin) (OEt2)2], (7Li, 13C, 15N), [(tmeda)2Li][P(SiH3)2], (29Si), [M(1,4,78,11-Me4-1,4,8,11-tetraazacyclotetradecane)(SCN)], (M = Li, Na; 7Li, 13C), [Li(glyH)(OH2)]+, (13C), [MePhLi(DME)], (13C), [(Bui2N2)BPHLi(DME)], (7Li, 11B, 13C), [(TMEDA)Li(PhP)2CSiMe3], (7Li, 13C), and [LiP(SiPh3)2 (THF)2], (7Li).

It has been...