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 n.m.r. 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 n.m.r. spectroscopy, silicon and phosphorus.

One book has been published which is relevant to this review: - 'Multinuclear Magnetic Resonance in Liquids and Solids - Chemical Applications', by P. Granger and R.K. Harris.

Several relevant reviews have been published, including 'N.m.r. properties of nuclei', 'Structural determination of inorganic compounds' 'Para hydrogen-induced polarization: a new spin on reactions with molecular hydrogen' 'Solid state and solution n.m.r. of nonclassical transition-metal polyhydrides', 'Metal n.m.r. of organometallic (d-block) systems', 'Two-dimensional n.m.r. and its application in coordination compounds', 'Chemistry in a spin: multinuclear magnetic resonance','Macrocyclic complexes of lanthanide ions', 'Structure, reactivity, spectra, and redox properties of cobalt(III) hexaamines', which contains 59Co n.m.r. spectroscopy, 'Diphosphazanes as ligands. Symbiosis of phosphorus chemistry and organometallic chemistry', which contains 1H, 13C, and 31P n.m.r. spectra, 'N.m.r. under high gas pressure', 'Nuclear magnetic resonance at high temperature', 'Alkali metal n.m.r. studies of synthetic and natural ionophore complexes','Behaviour of ion and water in lyotropic liquid crystals. N.m.r. study', 'Analytical chemical applications of high resolution solid state n.m.r. spectroscopy', and 'Nuclear magnetic resonance spectroscopy', which contains the application of pulsed 1H, 13C, and n.m.r. 29Si spectroscopy to the analysis of organosilicon compounds and polymers.

A number of papers have been published which are too broadly based to fit into a later section and are included here. The n.m.r. line shapes of double and triple quantum coherences have been calculated for spin 3/2 nuclei over a wide range of reorientation tirnes. A low temperature probe (1.2 K) for 1H, 2H, 3He, 11B, 13C, 19F, 27Al, 29Si, 115Sn, 117Sn, 119Sn, and 133Cs has been reported. The scope and limitations of the stepped frequency experiment have been investigated using 2H and 27Al n.m.r. spectroscopy. Qualitative models for 1H and 13C chemical shifts of interstitial atoms in clusters have been presented. A correlation of the 13C and 15N chemical shifts with compression has been demonstrated for interstitial carbide and nitride in transition metal clusters. Periodicities in the correlation of 11B, 13C, 15N, and 17O nuclear magnetic shielding and the correlation of interstitial atoms in metal clusters have been reported. 13C T1 values and chemical shifts have been determined for 19 selected organometallic half-sandwich and sandwich complexes of Cr, Mn, Fe, and Co. Large variations in T1 were found. New coordination modes of octafluorocyclo-octatetraene bound to Rh, Co, Ni, Pd, Pt, and Mn have been reported. The n'.m.r. spectra were reported. Results of relaxation in protein solutions and in silica particle suspensions show that the old and simple notion of bound water must be redefined to be of any help for interpreting relaxation results. 15C n.m.r. data have also been reported for (salicylidene -2-aminoacetophenone)-2-thenoylhydrazone complexes of VO, Mn, Co, Ni, Cu, and Zn, 2acetylfuran-2-thenoylhydrazone complexes of VO, Mn, Co, Ni, Cu, Zn, Cd, Hg, saccharin complexes of Mg, Zn, Cd, Hg, and Pb, R1C(SH)=NNCR2R3 complexes of Co, Ni, Pd, Cu, Zn, Cd, and Hg, and some thiocyanato complexes of Co, Ni, Pd, Cu, Zn, Cd, and Hg.

2 Stereochemistry

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

Complexes of Groups and IA and IIA. — Reviews entitled 'A review of 23Na nuclear magnetic resonance spectroscopy for the in vitro study of cellular sodium metabolism' and 'Nuclear magnetic resonance spectroscopy of chlorophyll' have appeared.

The IGLO method has been applied to calculate the C chemical shifts of numerous organolithium compounds. Homonuclear J(6Li-6Li) has been measured directly for E-2-Li-1-Ph-1-o-lithiophenylpent-1-ene for the first time using INADEQUATE. Theoretical calculations on allyl alkali metals have been used to discuss 1J (13C-1H). 1J(13 C-13H)has been measured on 1:1 adducts of ButLi and butadiene. 6Li and 13C n.m.r. spectroscopy has been used to examine 2-Li-C6 H4PPh2 in solution and it was concluded that it is a monomer. The low frequency shift of 6Li in (1) has been attributed to ring currents. The 13C n.m.r. spectrum was also reported. The 7Li n.m.r. chemical shift of [Li(dme) 2]+[1,2,4,5-(Me 3Si)4-benzenide] has revealed a large high frequency shift indicating anti-aromaticity. The 13C and 29Si n.m.r. spectra were also reported. The 7Li n.m.r. spectrum of [Ph3SnLi{NMe (CH2CH2NMe2)2}] shows the first recorded example of 1J(119 Sn-7Li) and 1J(117 Sn-7Li). The 23Na n.m.r. spectrum of [(C5Me5)Na] has a line width of 420 Hz which was attributed to the quadrupole relaxation due to the electric field gradient. The 13C n.m.r. spectrum was also reported. T1 and T2of 23Na in Na- have been determined. N.m.r. data have also been reported for [(1,4-Me2-1,4-diazacyclohexane)Li(μ-H) AlBut{CH(SiMe3)2}2], (13C), [(tmeda)LiCH-(SiMe2)2CH2], (13C, 29 Si), [(tmeda)LiCH(SiMe13