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, 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 demonstrated that double-quantum-filtered 23Na NMR spectroscopy may be used to estimate precisely the sodium ion concentration in a series of phantom models. 7Li, 23Na and 133Cs NMR spectroscopy has been used to study the effect of aliphatic chain length on alkali metal alkanoate melts in alkanoic acids. 1H and 23Na NMR relaxation has been used to study pectin solutions and gels. Double-quantum-filtered NMR spectra of 23Na in biological tissues have been analysed. Three-dimensional triple-quantum-filtered imaging of 0.012 and 0.024M 23Na has been achieved using short repetition times. Shift reagents can be used to identify intra- and extra- cellular sodium using double-quantum filtration 23Na NMR spectroscopy. The effect of Dy3+ on 23Na NMR in cell suspensions has been studied. The Jeener-Broekart experiment has been used to observe the 23Na NMR spectrum of Na+ ions that exhibit residual quadrupole splittings as a result of their interaction with ordered structures. Intracellular sodium in cardiomyocytes has been studied using 23Na NMR spectroscopy. Changes in intracellular Na+ concentration of erythrocytes from guinea pigs reared on low selenium cereals have been investigated using 23Na NMR spectroscopy. The response of the 23Na NMR double-quantum filtered signal to changes in Na+ ion concentration in model biological solutions and human erythrocytes has been studied. 7Li and 23Na NMR spectroscopy has been used to study Nitella cell walls before and after an ion-induced loss of the cationic exchange capacity 23Na NMR spectroscopy has been used to study the effects of deltamethrin on Na+ concentration in erthrocytes of rabbit. The mechanisms of ischemic myocardial injury in perfused rat hearts have been studied by 23Na and 31P NMR spectroscopy. Interleaved 23Na and 31P NMR spectroscopy has been used to study the effect of Na+ on cellular energy in ischemic rat heart. The inhibition of sodium influx and improved preservation of rat hearts during hypothermic ischemia by furosemide and bumetanide have been studied using 23Na and 31P NMR spectroscopy. A 23Na NMR study of intracellular Na+ in the prehypertensive rat kidney has been reported. 23Na NMR spectroscopy has been used to detect hypoxic injury in intact kidney, and the protection by glycine and alanine against hypoxic injury in the isolated perfused rat kidney. Double-quantum-filtered 23Na NMR spectroscopy has been used to study intracellular sodium in the perfused liver. 23Na NMR imaging has been used to investigate the distribution of brine in muscle. 1H and 23Na NMR studies have been carried out on the action of chlorpromazine and imipramine on nigericin-mediated Na+ transport across phosphatidylcholine vesicular membranes. The maintenance of the Na+ ion distribution in the arterial wall has been investigated using 23Na NMR spectroscopy. Factors affecting the 133Cs chemical shifts in erythrocytes from caesium fed rats have been studied. The use of dietary loading of 133Cs as a potassium substitute in NMR studies of tissues has been investigated. NMR data have also been reported for (7), (13C), [P[equivalent to]CS][Li(DME)2], (13C), [Li( 1,2:5,6-di-O-isopropyl-idene-α-D-glucofuranose)], (13C), [LiOSiMe2NMe2]6, (13C, 29Si), copolymers of 2-(1-naph-thylacetamidojethylacrylamide with acrylic acid and methacrylic acid, (23Na), poly(sodium 2-acryl-amido-2-methylpropanesulfonate), (23Na), and sulfonated polystyrene, (23Na).
The magnetic moment of 23Mg has been determined. Resolution enhancement in 25Mg NMR spectroscopy has been investigated. NMR data have also been reported for [Me2Al((µ-NPri2)2-MgMe]4, (13C, 27Al), [(Me2NCH2CH2CH2) Mg2Cl3 (THF)2]2, (13C), [(Me3Si)3CMg(μ-Br)3Mg(THF)3], (13C), (8), (13C), [{(Me13Sn)2Sn}2Ca]x4THF, (119Sn), [M(2,3-Me-1,4-Ph2-1,3-butadiene)(THF4)], (M = Ca, Sr; 14C), [(HC5Pri4)CaI(THF)], (13C), [M(η5-C5H4-CH2CH2OCH2CH2OMe)2], (M = Ba, Fe; 13C), and [(η5-CHPh4)2Ba(THF)], (13C).
The 19F NMR signal of (9) experiences large shifts upon coordination of metal ions such as Mg2+, Ca2+, Sr2+, and Ba2+. The displacement of calcium from osteocalcin at submicromolar concentrations of free lead has been investigated by 43Ca NMR spectroscopy. NMR data have also been reported for (10), [((R2N)MgMe}2 (Mg[N(SiMe3)2] [N(SiMe3)2AlMe3]}2], (13C, 27Al), [{HB(3,5-Me2pz)3}2M], (M = Mg, Ca, Sr; 13C), (11), (13C), [(THF)Mg(NPh)]6, (13C), [Mg(PhN=CPhCPh=NPh)(DME)2], (13C), [(4-ClC6H4CH2)Ph2COCa{N(SiMe3) 2}(THF)3], [IBa(OC6H2-2,6-But2-4- Me)(THF3)]2, (13C), Mg, Ca, Sr, and Ba salts of 3-NO2-1,2,4-triazol-5- one, (13C), [Ba(pz3BH)2(THF)], (11B, 13C), [Ba{N(SiMe3)2}{μ-N(SiMe3)}2Na(THF)2], (13C, 23Na, 29Si), complexes of Ba2+ and Pb2+ with (12), (13C), [Ba5(μ4-OH)(μ3-OCHMe- CH2NMe2)4(μ-dP)4(dpm)], (13C), [{PhC(O)CHC(O)CH=CHC6H4-4-NMe2}2Be]> (13C), [{(py)2Li}2(μ-Mg)( (Ph2SiO)2O} {(Ph2SiO)3O}], (29Si), [BaiOBut)2HOBut)2]4, (13C), [{C3F7C(O)CHC(O)C3F7}2(te traglyme)Ba], (13C), Ca2+ complex of nicardipine, (13C), [M(ESi(SiMe3)3}2Ln], (M = Mg, Ca, Sr, Ba; E = Se, Te; 77Se, 125Te) selenomethionyl calmodulin, (13C, 77Se), and calmodulin, (113Cd).
