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(SiMe13p-But-calix[4]arene-H)(MeCN)], (133Cs).

6Li and 15N n.m.r. studies with [6Li]-Li(2,2,6, 6-tetramethylpiperidide) and [6Li, 15N]-Li (2,2,6,6-tetramethylpiperidide) have supported an earlier suggestion that Li(2,2,6,6-tetramethylpiperidide) exists as a dimer-monomer mixture in THF. 6Li and 15N n.m.r. spectroscopic studies on [6Li, 15N]-LiNPri2 have shown that [6Li]-lithium pinacolate forms a 1:l cyclic mixed aggregate with LiNPri2. Two dimensional 6Li-1H heteronuclear Overhauser enhancement spectroscopy has been applied to Li+ complexes of lasolocid A. A 23Na triple quantum dynamic shift has been observed for the Na+ complex of 4,7,13,16,21-pentaoxa -1,10-diazabicyclo-[8.8.5]-tricosane. The influence of cysteamine on the entropy of fluctuations in DNA thermal trans-conformation has been studied by Na n.m.r. spectroscopy. CsBPh4 dissolved in pyridine has been studied by 133Cs-1H HOESY. N.m.r. data have also been reported for [But2NLi], (6Li, 13C), [Li{N(CH2CH2 NMeCH2-CH2)3N}]+, (13C), [M{1,4,7-tris(pyrazol-l-ylmethyl)-1,4, 7-triazacyclononane}]+, (M = Li, Na; 7Li, 13C, 23Na), [LiN(SiMe3)(2, 6-Pri2C6H3)]2, (7Li>, [PhSi{N(2,4,6-But3C6 H2)}2Li(solvent)], (13C, 13Si), [(THF)2Li{N(=C=C[BH3]PPh 3)}2Li(THF)2], 7(Li, 11B, 13C), (3), (7Li),[M{N(SiMe3 )}2)SPh] 2, {M = Li, (THF)Cs; 7Li, 13C, 29Si, 133Cs}, (4), (7Li, 13C), [{MeN-(CH2CH2 NMe2)2}LiNButCPh=Ni(η 2-C2H4)2], (13C), and [(THF)2LiN(SiBut2F)SiBu t2Me], (7Li, 13C. 29si).

The pharmocokinetics of Li+ uptake in the brain and muscle have been measured by 7Li n.m.r. spectroscopy. Multiple quantum filtered 23Na n.m.r. spectroscopy has been explored in model systems. Triple quantum 23Na imaging has been reported. Soy sauce has been investigated by 13C and 23Na n.m.r. spectroscopy. 23Na n.m.r. spectroscopy has been used to measure intracellular Na+ in hearts, red blood cells, kidney, liver, and muscle. The effect of head-group structure and counterion condensation on phase equilibria in anionic phospholipid-water systems has been studied by 2H, 23Na, and 31P n.m.r. spectroscopy. The Burg maximum entropy method has been applied to estimate 29K n.m.r. spectra of mung bean root tips. The complexation of K+ by tetraglyme and 18-crown-6 has been investigated by 39K n.m.r. spectroscopy. N.m.r. data have also been reported for [LiOCMe2Ph]6, (7Li, 13C), [As(RCO)2Li(THF)2], (13C),[PhOLi.hmpa] 4, (7Li, 31P), [LiO-2.6-Me2 -C6]H3]2, (6Li, 7Li, 13C), [Li(μ-OSiPh3) (η2-DME)]2, (13C), [M(OBut) ]4, (M = K, Rb, Cs; 13C), and [RCO2CS], (133Cs).

The purity of Grignard reagents has been assayed by 13C n.m.r. spectroscopy. 14N, 15N, and 17O n.m.r. spectroscopy has been used to study the mode of binding of some amino acids to Ca2+ N.m.r. data have also been reported for (5), (13C), [(C8H17)2Mg], (13C),[CH2=CHMgBr(THF)], (13C), [(ButC5H4)2M], (M = Mg; Hg; 13C), [2-MeOCH2CH2OCH2C 6H4M], (M = MgBr, HgBr, SnMe3; 13C), [(1,2-C6H4)Mg(THF)14, (13C), [Ca{CH(SiMe3)2}2 (THF)3], (13C),[Ca(Sn{CH(SiMe3) 2}2)2], (13C, 29Si, 119Sn), [M{N(SiMe3)2}2], (13C, 29Si), (6), (M = Mg, Zn; 13C), Ca2+, Sr2+, and Ba2+ complexes of H2NCH2CH2OCH2CH2 OCH2CH2NH2, (13C), [Ba(ButC(O)CH-C(O)But}2(NH3) 2]22, (13C), [Ba{N(SiMe3) 2}2], (13C),[Ba{N(SiMe3) 2}2](THF)2], (13C), [Ba(2,6-But2C6H3O)2 (HOCH2CH2NMe2)4]. 2C7H8,13(C),[Ba{N(C2 H4O)(C2H4OH)2}2], 13(C),[Be(2-OC6H4CO2) (H2O)2], (9Be), [Mg(adeny1ate kinase) (ATP)], (25Mg), Ca+2 complex of EtC{CH2O(CH2)n,CONHCHBut CONEt2}3,(13C), Ca2+ complexes of l-Ph-3-Me-4-acylpyrazolone-5, (13C), [Ba(O(CH2CH2O)n,CH3} 2], (n = 2 or 3; 13C), [Ba4 Ti13(μ3-O) 12 (μ 5-O) 6(μ 1-η1-OCH2 CH2OCH3)12(μ1, μ3-η2-OCH2CH2 OCH3)12], (13C, 17O), [KBa2(OSiPh3)5(CH3 OCH2CH2OCH3)2], (13Si), [Ba4Q(μ4-O) {μ2-OC6H2(CH2 NMe2)3-2,4,6}6], (13C), [Ba(18-crown-6)(hfac)2], (13C), and [Ba(2,5,8,11,14-pentaoxaheptadecane)(acac) 2], (13C).

Complexes of Groups IIIA, the Lanthanides, and Actinides.---A review entitled 'Solution chemistry of dioxouranium(VI) ion' which contains n.m.r. spectroscopy has appeared.

Magnetic moments have been measured for 91mY, 95Zr, and 97Nb. N.m.r. data have also been reported for [{Y(η5-C5 Me5)OC6H3But2} (μ-H)]2, [Y(η5-C5Me5) {CH(SiMe32}(OC6H3 But2)2], (13C, 29Si, 89y), [(Y(η5-C5Me5) 2Sm(μ-H)(μ-CH2C5H4-η 5)Sm(η5-C5Me5)] (13C), [(MeCN)4-Yb{μ-H)3BH} 2](13B), [(octaethylporphyrin) Y(μ-Me)2AlMe2], (13C), [(η5-C5Me5)2 Sc-[equivalent to]CH], (13C) [(η5-C5 Me52La(μ-η1,η3 -C4H6)La(η5-C5Me52(THF)], (13C), [(η5-C5 Me52-MCH(SiMe3)2], (M = Y, La, Ce; 13C), [(η5-C5 Me5)3Sm(C8H8)], (13C), [Yb({Sn(CH2-CMe3)3} 2(THF) 2], (13C, 119Sn, 171Yb), and [(η5:η5 -C13H20)Yb(THF)2], (13C).