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 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 = Rb, Cs; 29Si).
(6,7Li chemical shifts have been computed by the IGLO method for several LiCl oligomers with TMEDA, but only differ slightly. The structure of lithiated P-Ph2Me(N-Ph)phosphazene has been investigated by 1H, 6Li, 13C, 15N, and 31P NMR spectroscopy, including two-dimensional HOESY. NMR data have also been reported for [(Pri2NLi) (Me2 NCH2)2CHOLi}]2, (6Li), [(cyclohexyl)2NLi]4, (7Li), (3), (29Si), (R)-C5H10NCH2 CHPhLiCH2But, (6Li, 15N), [Li4(NBut)6Te2], (7Li, 125Te), cis-[Li(μ-NButCHBut CHNBut)2, (7Li), [{Li(NBut CHButCH2-NBut)AlH2}4], (7Li), [(PhSiNR)2Li(NR)2]Li(THF)4], (7Li, 29Si),[Me3Si(Li)NN(Li)SiMe3], 4(7Li, 29Si), [(Me3SiO) Me3-nSi(NLiSiMe3)n), (7Li, 29Si), [Me2ButSiNLiSiR1 R2NLiSiButMe2]2, (7Li, 29Si), [MeSi(SiMe2NLiR)3], (R = But, p-tol; 7Li), [RC(CH2NSiMe3)3 SnM(CO)2(η5-C5H5)], [HC{SiMeN 2N(p-tol)}3Sn][Li(THF)3], (M = Fe, Ru; 7Li, 29Si), [HC{SiMe2N(2-MeC6 H4)}3M][Li(THF)n], (M = Sn, Pb; 7Li, Si), (4), (7Li), [Ph4 P2N4(SR1)(SR2)LiI(THF)], (7Li), [(Salpan)AlLi(THF)2]2, (SalpanH 4 = (5); 27Al), and (6), (7Li, 29Si).
A molecular dynamics simulation of nuclear spin relaxation of 7Li+ in water has been published. 1H, 6Li, 7Li, and 13C NMR spectroscopy has been used to study the polymerisation initiating centres of But 2-Li-isobutyrate, LiOBut, and Li 3-Me-pentan-3-olate. Microemulsions as media for the destruction of organohalide pollutants have been investigated by 7Li NMR spectroscopy. The solubilisation of poly(ethylene oxide) in a lamellar phase formed by sodium bis(2-ethylhexyl) sulfosuccinate in water has been studied by 2H and 23Na NMR spectroscopy. Na NMR spectroscopy has been used to study the morphology of lightly sulfonated polystyrene. NMR data have also been reported for [Li(DME)2][Mn(NBut)2 (μ-NBut)}2], (7Li).
The flip-angle-independent experiment has provided transverse relaxation data for 23Na, even when used in conjunction with a coil that produces a very inhomogeneous B1 field. A method of extracting homogeneous 23Na NMR linewidths from two-dimensional Jeener-Broeckaert spectra has been described. Intracellular lithium in erythrocytes, hepatocytes, and fibroblasts has been investigated using 7Li NMR spectroscopy. Three-dimensional triple-quantum filtration 23Na NMR imaging has been reported. A Na NMR study of intracellular sodium in vascular endothelial cells has been published. A 23Na+ counterion NMR study of the behaviour of native xanthan in the biphasic region has been reported. 23Na NMR spectroscopy has been used to study the importance of coulombic end effects on cation accumulation near the oligoelectrolyte B-DNA. 23Na, 31P, and 59Co NMR spectroscopy has been used to study cold ischemia, using [Dy(TTHA)]3- and [Co(CN) 6]3- as markers. An extracellular contribution from a second-rank tensor to the double-quantum-filtered 23Na NMR spectrum in the isolated perfused rat heart has been detected. A 31P NMR and triple quantum filtered 23Na NMR study of inhibition of Na+/H+ exchange on intracellular sodium and pH in working and ischemic hearts has been reported. 23Na and 31P NMR spectroscopy has been used to study ischemia-induced ventricular fibrillation. 23Na NMR spectroscopy has been used to determine Na+ in beating rat hearts. Energy metabolism, intracellular Na+ and contractile function in isolated pig and rat hearts during cardioplegic ischemia and re-perfusion have been studied using 23Na and 31P NMR spectroscopy. Increased myocardial cellular 23Na NMR signals in perfused guinea pig heart induced by dihydro-ouabain and grayanotoxin-I have been measured. 19F, 23Na, 31p and 39K NMR spectroscopy has been used to study cationic and energetic alterations with oxidation stress in the perfused heart. 31P NMR spectroscopy has been used to investigate contractile dysfunction caused by normothermic ischemia and KC1 arrest in the isolated pig heart. Pathways of Rb+ influx and their relation to intracellular Na+ in the perfused rat heart have been investigated by 23Na and 87Rb NMR spectroscopy. K+-ribosome interactions in the cytoplasm of Eschericia coli K-12 have been studied using 39K NMR T2 measurements. 87Rb NMR spectroscopy has been used to investigate the effect of Na+/K+ pump activity on the intracellular Mg2+ regulation in guinea pig taenia caeci.133Cs Relaxation times have been measured in rat tissues.
1H and 13C NMR spectra of autoxidation products of 13(2)(R)-chlorophyll α have been fully assigned using two-dimensional HMQC and HMBC techniques. Calcium-coordinated water in calbindin D-9k has been determined using water 2H and 17O nuclear magnetic relaxation rates. NMR data have also been reported for [Mg(AlH4)2], (27Al), [M(BH4) 2L], {M = Sr, Ba; L = (THF)2, (diglyme)2, 18-crown-6; 11B), [(MeNCH=CHNMeCH)3Be]+, (9Be, 14N), [(Me2N-CH2 CH2C5Me4)MgX]2, (X = Cl, Br; 25Mg), [(THF)4Ba(Sn[P(SiMe3)2] (PSiMe3))2], (29Si, 119Sn), [{(Me3Si)2E)2Mg(THF)2], (29Si), [(Me3Si)2NCa{μ-P(SiMe3) 2)Ca2{μ-P(SiMe3)2-SnP (SiMe3)2], (119Sn), and [Ba(OSiBut2(CH2)3NMe2){N(SiMe3)] 2) (29Si)
Complexes of Group 3 and the Lanthanides. — The adduct [(η-5C>)5Me>)5)>)2Yb ((μ-H)(μ-CH>)3)Pt(Pri2 PCH2CH2PPri2)] shows 1J(171Yb1H) = 168 Hz and 1J (195Pt171Yb) = 960 Hz. The 89Y NMR spectrum of [Y(N(CH2CH2 OCH2CH2OCH2CH2)2N) CH2SiMe3)] shows coupling to the CH2 protons. 1J(89Y13C) = 39 Hz. The 29Si NMR spectrum was also recorded. 1J (89Y13C) has been observed for [(η 5-C5Me4Et)2YN(SiMe3) 2]. The 1H and 13C NMR spectra of [η5-2,4-Me2C5H5) Lu(η:η3-MeC5H5CH2 CH2CHMeC3H3Me)] have been completely assigned using two-dimensional NMR spectroscopy. The 171Yb chemical shifts for [(η5-C5Me5)Yb {1,2-(Me2P)2C6H4)2], [(η5-C5Me5)Yb(OPMe3) 2], and [(η5-C5Me5) Yb(Me2PhPCHSiMe3)2] have been measured using J(171Yb1H). The reaction between La(NO3)3.6H2O and 2,2':6',2"-terpyridine in MeCN has been investigated by 1H, 17O, and 139La NMR spectroscopy. The rotational correlation times of [La(EDTA)]- and [Co(en)3]3+ have been measured as a function of solution viscosity using 2H NMR relaxation measurements. An NMR conformational study of lanthanide(III) complexes with 1,4,7,10-tetraazacyclododecane-N,N',N",N'"-tetraacetic acid has been reported. A 17O and 31P NMR study has shown that there are only marginal differences between [La(NTA)(P3 O10) and [La(EDTA)(P3O10)] regarding complex geometry. NMR data have also been reported for [(Et2O)3 Li(μ-Cl)Y{CH(SiMe3)2}3]. (7Li, 29Si), [Ce(η5-C5H3 (SiMe3)2-1.3]2(μ-OMe)]2, (29Si), [η8-C8H8)Tm {4-PhC(NSiMe3)2))], (29Si), [Li(Yb[N (SiMe3)2]3)(tmen)], (7Li, 29Si), [Sc(N(CH2CH2N=CHC6 H2-2-O-5-Me-3-CH=NHCH2CH2)3N)], (45Sc), [{HB(3,5-Me2-pz)3}Sm(η 2-O2)], (11B), [MCl3-n (Sn2(OPri)9}]n, (M = Y, La; 119Sn), and [Yb(OC6H2But2-26-Me-4) 2 (THF)3], (171Yb).
