CHAPTER 1
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 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 Spectroscopy of the Non-metallic Elements', by S. Berger, S. Braun, and H.-O. Kalinowski. A number of reviews have also been published: 'Quantum Mechanical Exchange Coupling in Polyhydride and Dihydrogen Complexes', 'Proton transfer and hydrogen bonding with transition metal atoms and hydride hydrogen by IR and NMR studies', 'Problems of unusual hydrogen bonds between proton donors and transition metal hydrides and borohydrides', 'Endohedral metallofullerenes: structures and electronic properties', 'Proton tunnelling effects in metal hydride NMR', 'Application of polarization transfer and indirect detection NMR spectroscopic methods based on phosphorus-31 in organic and organometallic chemistry', 'Structure of Mo(VI), V(V), and Ti(IV) alkylperoxy and peroxy complexes deduced from NMR data and their reactivity', which contains 17O, 51V, 59Co, and 95Mo NMR data, 'Na NMR methods for selective observation of sodium ions in ordered environments', '31P, 13C, 1H, 23Na, and 59Co NMR spectroscopy of perfused organs', and 'High resolution NMR techniques in catalysis'.
A number of papers have been published which are too broadly based to fit into a later section and are included here. The temperature dependence of nuclear shieldings as well as isotope effects on shieldings have been computationally investigated for H2, HF, F2, CO, and N2. EHMO calculations have been used to correlate pz electronic densities of the aromatic carbon atoms in group VI metal-bis(η6-arene) complexes with the respective 1H NMR chemical shifts. Product-operator formalism has been applied to estimate J(IS) of the coupled nuclear spins I = ½ (1H) and S = 3/2 (11B) in Na2B12H11SH. A two-dimensional NMR approach to elucidating problems of structure and dynamics in chiral organometallic phosphine complexes has been suggested. The 13C NMR shifts of 5d transition metal carbonyls have been calculated with the inclusion of spin-orbit coupling. Chiroporphyrin metallic complexes have been used for NMR determination of the absolute configuration of amino acids. Analytical solutions for the relaxation times and lineshapes for I = 5/2 nuclei in biological systems have been published. 1H NMR spectroscopy has been used to determine the concentrations of CoII, CrVI, NiII, and PbII in water after solvent extraction using dithiocarbamate complexes. A high pressure NMR flow cell for the in situ study of homogeneous catalysis has been described.
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 – The 7Li NMR signals of BunLi/TMEDA and (1,3-cyclohexenyl)Li/TMEDA systems are at lower frequency than in the absence of TMEDA. The Li NMR spectra of complexes between chiral 3-aminopyrrolidine lithium amides and BunLi have been reported. A 1H, 6 Li HOESY NMR study of [(PhS)PhCHLi] has been reported and the NMR data used to probe charge distribution. NMR data have also been reported for [{Li(tmen)(AlH4)}2], (6Li, 7Li, 27Al), [(2,4,6-Me3C6H2) 2HGeLi•BuLi•OEt2], (7Li), [(BusLi) x-(BusMe2SiOLi)y], (7Li), [Li(NR1CR2=CHR3)(tmen)], (7Li), (1), (7Li, 29Si),[LiC{η3-N (SiMe3)CButCH2}]3, (7Li), [Li(C5H5-nRn)], {R = Me3 SiCH2, (Me3Si)2CH, Me2 ButSi, Me3Si, 7Li, 29Si}, [Li(dme)]2[1,4-(Me3Si)2C8 H6], (29Si), Li+ salts of dibenzo [a,g] corannulene anions, (7Li), (2), (7Li, 29Si), (3), (6Li, 29Si), (4), (6Li), [Li(THF)2 {Cu(CN)C6H3-2,6-(C6H2-2, 4,6-Pr13)2}]2, (7Li), [Li{BunC(NBut)2}]n, [PhBCl{C(NBut)Bun}], (7Li), and [KSi(SiMe3)3], (29Si).
4J 'W' coupling of 2.4 Hz is observed in [{CH2CButNHLi•HMPA}2] between the NH and one of the α-CH2 protons. NMR data have also been reported for (5), (7Li), [Me2Al{(PhCH2)N}2Li(THF)], (7Li, 27Al), [Li3Al2 (NHBut3- (NBut)3], (7Li), [Li{MeO-(R)-CH2CHPh} {(S)-CH3CHPh}N], (6Li),[Me3 SiNMeSiMeRMeLi], (7Li, 15N, 29Si), cis-[(MeSiNBut)2(NButLi•THF)], (29Si), [{(Me3Si)2N}LiMg], (7Li), [Li(Me2NCH2CH2NSiMe3)Li (µ4-Cl)Li(Me2NCH2CH2 NSiMe3)(THF)]3, (7Li), [Li (NRCPhNCPh=CR2)], (7Li), [SnCl (NRCPhNCPh=CR2)], (119Sn), [9-BBN-N (SnMe3)Li(pmdta)], (7Li, 11B, 15N, 119Sn), [Li{CE(NButBun}] 6, (E = O, S; 7Li), [Li4{(ButN) 3S}2], (29Si),[(Ph2NLi) 3LiCl(tmen)3], (7Li), [Li4 {(ButN)3S}2], (7Li), [C10H6{N[Li(THF)2]-SiMe3} {N(Tl)SiMe3}], (29Si), (6), (7Li), [Li2SO2(NBut)]n, (7Li),[Ph3P=CPhPPhLi], (7Li), [Li(PAr) 2SiR], (7Li, 29Si), [{Sb(PCy)3} 2Li6], (7Li),[M(THF)P(SiMe3) 2], (M = K, Rb, Cs; 29Si), [1(R),2 (S)-R2NCHMeCHPh0Li], (6Li, 15N), [(THF)2Li4M2(OBut)2 {(NBut)3S}2], (M = Na, K; 7Li), [Li(THF)4][(Me3Si)3CInBr3], (7Li, 29Si), [ArOLi]3, (7Li), [(ArO)2Sn], (119Sn),and But-2-Li-2,4,4-Me 3-glutarate, (7Li).
The lithium distribution in red blood cells has been investigated using 7Li NMR spectroscopy. 7Li NMR imaging has been applied to lithium in the brain and muscle of rats. The dipolar interaction of Na with hydrogen nuclei in glycerol solution has been measured. The phase diagram of a lyotropic mixture sodium bis(2-ethylhexyl) sulfosuccinate /dodecanol/water has been studied using 23Na NMR spectroscopy. Multiple-quantum filtered 17O and 23Na NMR analysis of mitochondrial suspensions has been reported. 23Na Double-quantum-filtered NMR spectroscopy has enabled the detection of anisotropic motion of Na+ due to their interaction with ordered structures in biological tissues. The feasibility of monitoring intracellular sodium changes using sodium triple quantum filtered NMR spectroscopy has been explored. 23Na NMR spectroscopy has been used to study Ca2+ damage in rat hearts. 23Na and 31P NMR spectroscopy has been used to investigate the mechanism of ischemic damage during preservation of the isolated pig heart. Reperfusion of rat hearts has been studied using 23Na NMR spectroscopy. The intracellular sodium concentration in perfused mouse liver has been determined by 31P and 23Na NMR spectroscopy. 23Na and 31P NMR spectroscopy has been used to study the influence of repeated ischemia/reperfusion cycles on human calf energy metabolism. 7Li and 23Na transmembrane cation transport mediated by the ionophore lasalocid A has been investigated. The ionophore properties of cationomycin in large unilamellar vesicles have been studied by 23Na and 39K NMR spectroscopy. Intracellular K+ during ischemia in the perfused guinea pig heart has been measured using K+ NMR spectroscopy. The kinetics of ATP-sensitive K+ channels in isolated rat hearts have been assessed by 87Rb NMR spectroscopy. Borocryptates of Cs+ and [NH4]+ in a nematic liquid crystal have been studied by 10B, 11B, 14N, and 133Cs NMR spectroscopy. 133Cs NMR spectroscopy has been used to study the uptake of Cs+ by the mycelium of the mushroom, Pleurotus astreatus.
The structures of [Sc2@C84] and [Ca@ C82] have been investigated using 13C NMR spectroscopy. 9Be and 27Al NMR shieldings have been calculated for [Be(OH2)4]2+, [Be (OH2)3(OH)]+, [Be3(OH) 3(OH)3](OH2)(OH2)6], 3+, [Be2(OH)2(OH2)4] 2+, [Al(OH2)6]3+, [Al (OH2)5(OH)]2+, and [Al2 (OH)2(OH2)8]4+. NMR data have also been reported for [Be{(Me2P)2C(SiMe 3)}2], (9Be), (7), (25Mg), [Ca2{Be2(OH)7} (H3O2)(OH2)2], (9Be), [Be3(µ-OH)3(OH)2) 6]3+ (9Be), [(BeOH)4(OH) 6]2-, (9Be), and [{(2,6-Pri2C6H3)N(SiMe3)SiO\ 3}2{(2,6-Pri2C6 H3)N(SiMe3)SiO2(OH)}2 {Mg(THF)}5], (29Si).
Complexes of Group 3, the Lanthanides, and Actinides – In Y{P(SiMe3)2}3], 1J (89Y31P) = 122.4 Hz for the terminal phosphorus and 56.7 Hz for the bridging phosphorus. The 19F T1 values of [UF6] and [SF6] have been used to determine the anisotropic intermolecular potential. NMR data have also been reported for [Sc2@C74], [Sc2 @C76], (45Sc), [Li(C5H4 CH2CH2PMe2)], (7Li), [La(C5H4CH2CH2PMe2) 3], (139La), [Ln2{1,4-(Me3Si) 2C8H6}3], (M = Ce, Nd, Sm; 29Si), [Yb{η5-1,3-(Me3Si) 2C5H3}2(18-crown-6)], (29Si, 171Yb), [(DMF)10 Yb2 {Pt(CN)4}3], (195Pt), (8), (29Si), [ScL{N(SiHMe2)2}], {H2 L = (9); 29Si}, [Yb(Ph2pz) 2 (DME)2], (171Yb), [{Yb(η2-Bu2 pz)(µ-η2:η2-But2pz) (THF)}2], (171Yb), [N(CH2CH2NSi Me3)3LaClLi(THF)3], (7Li, 139La), lanthanide complexes of 2,6-diacetylpyridyl bis(pyrazinecarboxylic hydrazone), (139La), [La{(O2CCH2)2NCH2 CH2N(CH2CO2)CH2CH2 N-(CH2CO2)CH2CH2N(CH2 CO2)2}]3-, (15N, 139La), and N-(2-acetyl-thiophenoimino)-2-benzamidoethanamide, (139La).
Complexes of Group 4 – NOE has been used to derive the solution structure of [{(Me3Si)2N}Zr(CH2 SiMe2NSiMe3){η6-PhCH2B (C6F5)3}]. In [{(η 5-C5H5)2M1} (µ-RCCH)(µ-C[equivalent to]CR)M2(η5-C5 H5)2]+, the CH group has a 13C chemical shift of 161.0 ppm with 1J(13C 1H) = 103 Hz. Exceedingly narrow 11B lines have been observed for [(Zr6BCl12)Cl6-n Ln] with 2J(31PZr11 B) = 8.8 Hz. NMR data have also been reported for [{η 5-1,3-(SiMe3)2C5H3} (c-C5H9)7Si8O13- Ti(CH2Ph) 2], (29Si), [Ti(NBut) {PhC(NSiMe3)2}(η3-BH4) (NC5H5)], (11B), (10), (11B), [(PhCH2)3Zr{η5-CH4B(C6 F5)3}]-, (11B), [(η5-C4 H4BC6F5){η5-1,3-(Me3Si) 2C5H3}Zr(C6F5) (OEt2)], (11B), [(Me2N)3MSi (SiMe3)3], (29Si), [(Me3SiO) 2Zr(SiPh2But)Cl•2THF], (29Si), [(η5-C5H5)2Ti(η 2-RC [equivalent to] CSiMe3)], (29Si), [{(η8-C8H8)Ti}2 (µ-η2:η2-Me3SiC+CSiMe3)], (29Si), [MeSi{Si-Me2N(C6H4Me-4)} 3MCo(CO)3L], (M = Ti, Zr; 29Si), [(η 5-C5H5)2Ti(N=C=NSiR3) 2], (29Si), [(η5-C5H4 SiMe2NRSiMe2C5H4-η5) MCl2], (M = Ti, Zr, Hf; 15N, 29Si), [{η 5-1,3-(Me3Si)22C5H3} {(C5H9)7Si8O13} TiX2], (29Si), [LZrCl2], {L = (11), 29Si}, [(η5-C13H8SiR2 C9H6-nRn-η5)ZrCl2], (29Si), [(η5-Me3SiMC4Me 4)(η5-C5Me5)HfCl2], (M = Si, Ge; 29Si), [(η6,η'6-Pr i2NBC6H4-4-CH2 CH2-4-C5H4BNPri2) ZrCl2], (11B), [Me3SiNRTiCl3], (11B, 14N, 15N, 29Si, 35Cl), (12), (pSi), [Ti6O4(O2 CCH3)4(OPri)12], (17O, 13C CPMAS), [TiO2(O2Si2Ph4) 2], (17O, 29Si), [Pb2Ti2 (O)(O2CR) 2 (OPri)8], (207Pb), [{Cd(OPri)3}Sr{Zr2 (OPri)9}]2, (113Cd), and [(TiCl4)2(Se2Me2)], (77Se).
