encser. P., Acta Chim. (Budapest), 77, 55 keleit. E.. Petitjean, C , Schneuwly. H . , H.,Eicher. H , Mayer, A,, J. Mol. Biol., (1973) Schroder. W U., Phys. Lett. 8 , 38. 64 7 0 , 665 (1972). Vertes. A , Ranogajec-Kornor M , Suba, (1972) Wolbeck, 6..Zioutas. K . , Nucl. Phys. A, M i b i d , 74, 159 (1972) Wappling. R , Haggstrom, L , Devanaray181,289 (1972) anan, S.. Phys. S c r . . 5, 97 (1972). Wolmarans, N S , deWaard, H , Phys. Viccaro, P J., Barros, F de S., OostWappling, R , Pernestal, K.. Nucl. I n Rev. C, 6, 228 (1972). erhuis, W. T , Phys. Rev. B, 5, 4257 strum. Methods, 109, 1 (1973) Woodhams. F. W. D . , White. P S.. Knop. (1972). Watanabe. N.. Niki, E , BuIl. Chem. SOC. 0..J. SolidState Chem.. 5, 334 (1972) Vincze, I . , Phys. Rev. E , 7, 54 (1973) Jap., 45. 1 (1972) Yagisawa, K , Phys. Status Solidi A, 16, Vincze, I . , Solid State Commun., 10, 341 Watt, J. P , Leiper. W.. Ade-Hall. J. M., 291 (1973) (1972) Goble. D. F., J. Geophys. Res., 78, 3301 Ibid., 18, 589 (1973) Vincze, I , Campbell, I A , J. Phys. F , 3 , (1973) Yakimov. S. S.. Ozhogin. V. I . , Gamlitskii, 647 (1973) Watts, J. C.. Huheey. J. E . , Chem. Phys. V. Ya.. Cherepanov, V M I Pudkov. S D , (808) Vincze, I , Cser, L , Phys. Status Solidi B. Lett., 14, 89 (1972) Phys. Lett. A , 39, 421 (1972). 49, K99 (1972) (809) Wegener, H H. F , Braunecker. B . , Ritter, Yamaguchi, K.. Yamamoto, H , Yarnaguibid.. 5 0 . 709 119721. G.. Seyboth. D . . Z. Phys., 262, 149 chi. Y , Watanabe. H.,J. Phys. SOC. Jap., Vincze,'l , Gruner, G . , Phys. Rev. Lett.. ( 1973) 33, 1292 (1972) 28, 178 (1972) Yamarnura. H., Kiriyama, R., Bull. Chem. Weihofen. U., Z. Naturforsch. A . 27. 565 Vlasov. A Ya., Gornushkina. N A , PeSOC.Jap., 45, 2702 (1972) (1972) trov, M . l , Izv Vyssh Ucheb Zaved, Fiz., Yamaoka, T I Mekata, M . , Takaki, H , J Welgehausen, K . , Rudee, M L . McLellan. No 5, 84 (1972) Phys. SOC.Jap , 35, 63 (1973) R B , A c t a Metal.. 21, 589 (1973) (794) Vogl, G , Schaefer. A,, Mansel, W , PreYassoglou, N . J , Nobeli, C., Kostikas, A., Wender, S A , Hershkowitz. N , Nucl. lnchtel, J . , Vogl. W., Phys. Status Soiidi E . Simopoulos, A , Soil. S o . SOC. Amer., strum. Methods, 98, 105 (1972) 59, 107 ( 1973) Proc., 36,520 (1972) Wender. S A Hershkowttz. N., Phys. Voronin, A M , lzv. Akad. Nauk Kaz. Yeats, P. A,, Sams, J. R , Aubke. F . . Rev. Lett.. 29, 1648 (1972). SSR, Ser. Fiz.-Mat., 1 0 ( 2 ) . 61 (1972). Inorg. Chem., 11, 2634 (1972) West, P , Nucl. Instrum. Methods, 101, Wagner, F. E , Dunlap, B D , Kalvius, G Yeboah-Arnankwah. D , Rev. S c i In243 (1972). M . . Schaller, H , Felscher, R . , Spieler. H , strum., 44, 225 (1973) Wickman, H. H I J. Chem Phys.. 56, 976 Phys. Rev. Lett., 2 8 , 530 (1972). Yushchuk, S I . , Kamzin. A. S.. lnorg. ( 1972) (797) Wagner, B N , Shive, P. N . , Allen, J L , Mater. ( U S S R ) ,9 , 477 (1973). Williamson, D L.. Bukshpan. S.. Ingalls, Terry, C.. J. Geomagn. Geoeiec., 2 4 , 353 Zasimov. V S.. Kuz'min, R N . , AleksandR . , Phys. Rev. B , 6 , 4194 (1972) (1972). rov, A. Yu., Firov. A I , JETP Lett., 15, Williamson. D L , Bukshpan, S., Ingalls, Wagner, F E.,Spieler. H , Kucheida, D , 277 (1972) R , Shechter. H . , Rev. S o . Instrum.. 43, Kienle. P , Wappling, R . , Z. Phys.. 254, Zasirnov, V S , Kuz'min. R N., Firov, A. 194 (1972) 112 (1972) I . , Sov. Phys -Crystallogr., 1 7 , 757 Window, 6.. "AIP Conf Proc -No. 5, Wagner, F. E , Thorna. K . . Atoji, M , Z. (1972) Magnetism and Magnetic Materials, SevPhys.. 262, 265 (1973) Zasimov. V. S., Kuz'min, R . N . , Lobanov, enteenth Annual Conference, Chicago, Wagner, F. E..Wortmann, G , Kalvtus, G N N , Firov, A . I , Vesfn. Mosk. Univ., 1971." C. D . Graham, Jr , J J. Rhyne. M . , Phys. Lett. A . 42. 483 (1973) Fiz., Astron.. 13. 725 (1972). Ed , American Institute of Physics, New Walch, P F . , Ellis, D E., Phys. Rev. B , 7 , (838) Zelentsov, V. V., Ablov, A. V., Turta, K. I , York. 1972, Part 1, p 522 903 (1973) Stukan, R A , Gerbeleu, N. V., Ivanov. E. Window. B , Phil. Mag., 2 6 , 681 (1972) Walter, H. K , Backe, H , Engfer, R . , KanV., Bogdanov, A P I Barba. N . A,, Bodyu, keleit. E , Petitjean, C., Schneuwly, H . . Window, B . , Phys. Rev. B. 6. 2013 V . G , Russ. J. lnorg. Chem.. 17, 1000 Schroder, W U.,Helv. Phys. Acta. 45. 47 (1972) (1972) (1972) Winterhalter, K H.. Dilorio, E. E , BeetleZioutas. K , Wolbeck, B , Perscheid. B , Walter. H K.. Backe, H., Engfer, R . , Kanstone. J G . , Kushimo. J B., Uebelhack. Z. Phys., 262, 413 (1973)
Nuclear Magnetic Resonance Spectrometry John R. Wasson and Diana K. Johnson Department of Chemistry, University of Kentucky, Lexington, Ky. 40506
This review covers the published literature from July 1971 to July 1973. Over 10,000 abstracts were screened in the course of preparation of this review. In order to keep the review within manageable proportions, considerable elimination of articles was necessary as in our previous effort to survey the NMR literature (I). The comprehensive nature of this review and space limitations prevent more than citations of specialized reviews, monographs, and texts and a selection of references related to specific areas of chemistry. Because of the vastness of the literature surveyed, many fine contributions have undoubtedly been omitted. We apologize to the authors whose publications were deleted and are extremely grateful to all who were kind enough to supply us with reprints of their work. It is hoped that where this review fails as a review, it succeeds as a useful guide to current advances and applications of NMR spectrometry in chemistry.
BOOKS AND REVIEWS A number of basic monographs and texts have appeared (2-5) as have texts dealing with PMR spectrometry in medicinal and biological chemistry (6),simple heterocyclic molecules (3, ferro- and antiferromagnets (8),metals ( 9 ) , sulfur compounds ( I O ) , theory of magnetic resonance 314R
(11, 12), I3C NMR spectra (13-16), fluorine chemical shifts (27),NMR shift reagents ( 1 8 ) , paramagnetic molecules (19, 20) and NMR spectral interpretation (21-24) and chemically induced magnetic polarization (25). Several review volumes (26-29) covering a variety of subjects have appeared, The Chemical Society (London) volume (29) being perhaps the most comprehensive of a continuing series. Several reviews concerned with applications of XMR to biochemistry and related subjects summarize recent advances (30-53). Reviews of a general nature (54-57, nitrogen NMR (Sa), pulse Fourier transform NMR (59, 60), nuclear shielding (61), spectral analysis ( 6 2 ) , nomenclature (63), inorganic compounds (64), high resolution NMR theory (65),NMR in combination with other methods (66),correlation tables (63, use of NMR in the forensic laboratory (68), pharmacology (69-71), and pesticide research (72), and NMR and ESR in liquid crystals (73) have also been presented. Several discussions of 13C NMR (74-80) in addition to the texts cited above have appeared. Spin-spin coupling (81, 82), spin-spin coupling between phosphorus nuclei (83), long range spin coupling (84),halogen hyperfine interactions (85),chemical shift correlations for chlorine-containing compounds (86) and chemical shift reagents (87-94) have been the subjects of some attention. The NMR spectra of annu-
ANALYTICAL C H E M I S T R Y , VOL. 46, NO. 5 , APRIL 1974
John R. Wasson is an assistant professor of inorganic chemistry at the University of Kentucky in Lexington, Ky. He was born in St. Louis, M o . , and received his education at the Universlty of Missouri at Columbia (BS. 1963; MA, 1966) and Illinois Institute of Technology (PhD, 1970). In 1969 he joined the faculty of the University of Kentucky. He has published several technical papers and has authored six chapters on preparative inorganic chemistry for Mefhodicurn Chimicum Houben- Weyl. His oublications and research interests are in the areas of transition metal chemistry, electron paramagnetic resonance and nuclear magnetic resonance spectrometry, and semiempirical molecular orbital theory. He is a member of the American Chemical Society, the Chemical Society (London), Phi Lambda Upsilon, and the Kentucky Academy of Science.
Diana K. Johnson is a graduate student in chemistry at the University of Kentucky. She received her BS degree in chemistry from the University of Kentucky in 1973. Her particular research interests include magnetic resonance SpeCtrOSCOpy and studies of biologically significant inorganic compounds. She is a member O f the American Chemical Society and the coauthor of several scientific articles.
of papers dealing with carbon-13 chemical shifts and coulenes (95),polymers (96-104),NMR determination of oppling constants. The referencing of 13C chemical shifts tical and enantiomeric purity (105), applications of NMR (263, 264), correlations of ESCA and I3C NMR shifts in organic chemistry (106), NMR spectra of acridines (265-267) and numerous cheoretical and experimental (2077, N-containing compounds (108), and heterocycles studies of 13C chemical shifts and coupling constants (log), double resonance (IIO-II3), the nuclear Ov(268-278)have been reported in addition to purely experierhauser effect ( I 24), dynamic nuclear polarization (115mental work. 117), NMR and ultraslow motions (118), NMR a t high magnetic fields (119,120), continuous-wave NMR techSPIN-SPIN COUPLING CONSTANTS niques (121),relaxation (122),solvation of ions and ion pairs (l23), solvent dependence of nuclear spin-spin Theoretical calculations of spin-spin coupling constants coupling constants (224),NMR of gases (125),medium continue to be of interest. Empirical (279),INDO and effects (126),high pressure NMR relaxation studies of liqCNDO molecular orbital (280-283),nonempirical (284), uids (127),bandshape phenomena for fluids (128),NMR maximum overlap (285),and other (286-289)calculations a t zero frequency (129),NMR of molecules oriented in have been reported, although this selection of papers is far electric fields (130)and oriented on solids (131)have all from exhaustive. Anisotropies of spin-spin couplings (290, been reviewed. The NMR spectra of solids (1321,super291), effects of a-substituents on benzylic spin-spin couconductors and dilute alloys (133),water and ice (134), plings (292)and isotope substitution (293),relaxation and ferromagnets and antiferromagnets (135),NMR and conintensities of hyperfine structure lines (294,295), determiformational motion in solids (136),nuclear spin diffusion nation of signs and relative signs of coupling constants (1377,application of NMR in stereochemical determina(296-300),long range spin coupling (301-324),sigma and tions (138)and isomerism problems (139),NMR of nitropi contributions to coupling constants (325-327, spingen (140),silicon (14I),phosphorus (142-146)and pentaspin coupling constants in a variety of phosphorus comcoordinated compounds ( 1 4 7 , transition metal hydrides pounds (328-335) as well as numerous other com(148),tris(ethy1enediamine) complexes (149),organolithipounds (336-340)have been considered. um compounds (150), and organometallic and coordination compounds (151-154)have also been surveyed. A few MULTIPLE RESONANCE, SPIN ECHOES, CIDNP, other reviews are cited in the following sections. AND PULSED RESONANCE AND FOURIER The thesis literature remains probably one of the best TRANSFORM METHODS sources of detailed syntheses, discussions and experimental details. M.S. level theses describing NMR studies RDouble resonance studies of organoselenium compounds thioglycolic acid corrosion inhibitors (155) and paramag(341),solvent effects on trimethylchlorostannane (342), netic amine adducts of nickel(I1) dithiophosphates (156) pentafluoropyridine (343),organophosphorus esters (344), as well as many others dealing with topics in NMR spec6-methyldecaborane (345), fluorocarbons (346), trichlotroscopy are available. Unfortunately, these are not abroethane and dichloroethane (347), substituted ammostracted as are doctoral studies in Dissertation Abstracts. nium ions (348), partially aligned molecules (349,333, References 157-190 represent a brief selection of dissertaand 2-bromothiazole (351) have been reported as have tions which may be of general interest. theoretical considerations (352-356) and experimental techniques (357,358). CHEiMICAL SHIFTS Spin-echo techniques in the Earth’s magnetic field range (359), new techniques of spin-echo observations The analysis of NMR spectra of a variety of systems (360), Fourier transform spin-echo spectroscopy (361), (191-204),particularly ABMX NMR spectra (195, 196, moments of echo lines (362),photo echo-nuclear double 200), MO calculations of chemical shifts and coupling resonance in ruby (363),spin-echo studies of solids (364constants (205-213),relativistic generalized Breit correc376), benzene absorbed on silica (377),liquids (378-384). tions to the Fermi contact equation (214) and the relasolutions containing Ni(I1) and Co(I1) ions (385,386) and tions between ESCA and NMR chemical shifts (215,226) helium-3 gas (387) have been reported. Various applicahave been explored. Gas to liquid shifts of nonpolar moletions of the spin-echo method to chemical kinetics have cules (2177, theory of 31P chemical shifts (218),anisotropbeen described (388-390). ic 59C0 chemical shifts in C o z ( C 0 ) ~(219),I7O chemical Several reviews of chemically induced dynamic nuclear shifts and hydration rates of cyclic ketones (220),correlapolarization (CIDNP) have appeared (391-396) as have tions between 13C and chemical shifts for a variety of discussions of theoretical aspects of CIDNP (397-405). tetracoordinate boron compounds (221) and evaluation Photochemical reactions leading to CIDNP can be studied and calculations of fluorine-19 chemical shifts and couconveniently in conventional NMR spectrometers (406). pling constants (222-226)have been discussed. The use of An undergraduate laboratory experiment (407), CIDNP in factor analysis in solvent effect studies ( 2 2 7 , ring current effects (228-2321, long-range shielding effects (233-235) the presence of paramagnetic shift reagents (408),and numerous CIDNP studies have been reported (409-448). and numerous calculations of proton chemical shifts and Spectrometers for multiple pulse NMR (449)have been coupling constants and correlation of proton chemical reviewed and additional improvements and modifications shifts with molecular properties (236-262)have been re(450-453),particularly with regard to sulfur-33 investigaported. tions with a superconducting solenoid (452),have been Consistent with the increasing availability of XMR suggested. Quantitative aspects of coherent averaging spectrometers for carbon- 13 measurements is the plethora A N A L Y T I C A L CHEMISTRY, V O L . 46, NO. 5, A P R I L 1974
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(454), and calculation of response in pulsed NMR experiments (455) have been considered along with studies of ion-exchange resins (456), striated muscle ( 4 5 3 , lyotropic liquid crystals (458), crystalline polymers (459), the uncured diglycidyl ether of bisphenol A (460), rotational diffusion in perchloryl fluoride ( & I ) , measurement of correlation times (462),and viscous liquids (463). Fourier transform NMR spectrometry has been explained by analogy with a resonant tuning fork (464), reviewed (465), and numerous experimental and theoretical considerations elucidated (466-487). Lead-207 pulse Fourier transform NMR spectrometry promises to be a n extremely useful tool in lead chemistry (488). Carbon-13 Fourier transform NMR spectra have been of particular value with studies of porphyrins (489), heparin (490), quinoline (491), and branched-chain carbohydrates (492). Partially relaxed boron-11 Fourier transform NMR spectra of n-nonaborane(14) (493) and silicon-29 Fourier traqsform NMR spectra (494) of T M S and related compounds have been described.
RELAXATION Among relaxation studies, those of particular interest include measurement techniques (495-502), theoretical considerations (503-517), band shapes (518, 529), and studies of relaxation in liquid crystals (520-524), gases (525, 526), adsorbed gases (527), lithium-7 organometallic compounds (528),water protons in tissues (529), ammonia and metal ammonia solutions (530, 532) carbon disulfide (532), halocarbons (533-*539), aromatic compounds (540542), polymers (543, 544), phosphorus compounds (545548), solid tin(lV) hydride (549), lithium halides with pyridine in aqueous solution (550), hydrogen bonded liquids ( S I ) , aliphatic amides and oximes (552), hydrocarbons (552'), clathrated sulfur hexafluoride (553), tetramethylammonium halides (554), and methyl' nitrate (555). Nuclear spin lattice relaxation time due to orbital interaction (533, transverse cross relaxation in liquids (557), and tunneling motions (558-560) have also received attention. NUCLEAR OVERHAUSER EFFECT The application of the intramolecular nuclear Overhauser effect in structural organic chemistry (561); and in solutions of organic free radicals (562) have been reviewed. 'The nuclear Overhauser effect in the NMR spectra of paramagnetic crystals (563), carbon-13 spectra (564), hexamethylphosphoramide solutions of alkali metals (5gt5), nitroxide radicals (366, 567), aqueous potassium fluoride solutions (n'6H),formato and formamido complexes of pentamminecobait (111) (5654, steroids (570), formylpyrroles ( 5 7 2 ) , purine nucleoside glycosyl (5721, and associated (573. 574); and macromolecular systems (575) has been reported. Reporti of the intermolecular nuclear Overhauser effect (576,,577, influence of paramagnetic species on the internucleai Overhauser effect (578), determination of nuclear Overhauser enhancement factors from NMR spinlattice relaxation rates (579), the Overhauser effect in a weak or quasinull field (580)as well as quantitive application of the determination of molecular structure (581)are available. An experiment suitable for demonstration of the nuclear Overhauser effect a t the undergraduate level has been described 1582). LIQUID CRYSTALS I'sw of liquid crystals in NMR spectrometry has been the subject of a number of reviews (583-586), and nuclear relaxation in liquid crystals (587) has been reviewed. The review of experimental angular correlation functions of molecules in liquids and in crystals by Keller and Kneubuehl (588) should also be of interest to those concerned with descriptions of spectra in liquid crystals. Phase diagrams of liquid crystal solvents used in NMR studies have been reported (589). Reformulation of NMR theory for liquid crystals (590), influence of vibrations on molecular structure determinations from NMR in liquid crystals (592, 592), and other parameters of nematic liquid crystals (593) have been discussed. A related study of molecular alignment in dipolar liquids (594) has been presented. Investigations of the anisotropy of indirect spin316R
spin coupling constants on molecular structure determination using nematic solvents (595): angular dependence of spin-lattice relaxation times in liquid crystals (596), intraand intermolecular contributions to proton relaxation in liquid crystals ( 5 9 3 , bromide-81 ion binding (598) and catalysis in liquid crystal phases (599) have been described. NMR studies of poly-y -benzyl-L-glutamate in static electric fields (600), various cholesteric compounds (601), proton resonance lineshapes in lamellar liquid crystals (602) and sodium-23 in macroscopically aligned lamellar mesophases (603) have -been reported. Investigations of variable frequency pulsed NMR (604), nitrogen-15 labeled formamide (605), p-dithin (606), ethylene carbonate and monothiocarbonate ( 6 0 7 , D2O (608), paraffinic chain motions (609), furan and thiophene (610), methyl halides (612), amphiphiles (612), and sodium-23 ions (623) have been reported for lyotropic liquid crystal systems. Relaxation in nematic phase liquid crystals (624-616) has been described as have studies of the following molecules oriented in the nematic phase: ethylene sulfite ( 6 1 7 , ethylene oxide and sulfide (628) ethylene carbonates and thiocarbonates (629-621), substituted benzenes (622-632), cyclopropane (632), cyclobutane (633), 1,3-butadiene (634), trimethylene oxide (635), deuterated methanes and 2,2dimethylpropane (636), norbornadiene (637), quinoxaline (638), 1,l-difluoroethane (639), 1,2-difluoroethane (640), 3,5-dichloropyridine (642), y -picoline (642), anisylidene p-aminophenyl acetate (643), dimethylformamide (644), 1,4-naphthoquinone (645), butadiene sulfone (646), thiohene (647) 1,4-dioxin and 1,4-dithiin (648), thieno[2,3{]thiophene (649), 2,1,3-benzothiadiazole (650), 2-furaldehyde (651), phthalazine (652), furan- and thiophene2,5-dialdehydes (653), acetonitrile (654), acetone (655), tropone (656), 3,3'-biisoxazole (657), P-propiolactone (658),1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane (659), methylmercuric halides (660), r-cyclopentadienylmanganese tricarbonyl (662), and the hydride cluster, H~RuQ C0)6C(CH3) ( (662).
SOLID STATE NMR studies of molecular motion in solids (663), narrowing of NMR spectra of solids by high speed specimen rotation (664), interpretation of magnetic resonance measurements in metals (665), and pulsed NMR in solids (666) have been reviewed. Second moment expressions for solids containing reorienting nuclear spins (667) have been derived, and NMR spectra of rapidly rotated solids containing reorienting molecular groups have been considered theoretically (668). The carbon-13 NMR of adsorbed molecules (669) and organic solids (670), ethylene adsorption by sodium and calcium forms of Zeolite Y (671), and determination of the ground state configuration of a n orthohydrogen molecule in solid parahydrogen (672) have been described. Of the hundreds of NMR studies of alloys and other solids, the ones concerning vanadium sulfides (673) chromium(II1) bromide (674, 675), chromium dioxide (676), rubidium trifluoromanganate (677,tetramethylammonium manganese chloride (678, 679), cesium trichloromanganate dihydrate (680), potassium ion fluoride (681), potassium ferricyanide (6821, cobalt-59 NMR in tricobalt tetroxide ( 6 8 4 , cobalt(I1) chloride dihydrate (684, 685), tricobalt tetrasulfide (686), cobalt manganese nonacarbonyl ( 6 8 3 , potassium hexacyanocobaltate(II1) (688, 689) and studies of cobalt lanthanum magnesium nitrate tetracosahydrate (690), rubidium tetrafluorocobaltate(I1) (691), C O ~ ( C ~ H ~(692), ) & hexahydrated and fluorides of cobalt(I1) and nickel(I1) (693), Ni(NH3)2Ni(CN)4.2C6H6 (694), copper(1) salts (695, 696), KCuF3 and K2CuF4 ( 6 9 7 , C U ( N O ~ ) ~ . ~ .(698. ~ H ~699), O copper(I1) chloride dihydrate-d4 (700),tetrahalocuprates(I1) (702, 701'), copper(I1) formate tetrahydrate (702), europium(I1) oxide (703), sulfide (704), and selenide (705, 706), rare earth trifluorides (707),lanthanum deuterides (708), rare earth substituted lanthanum trichloride (709),polycrystalline uranium hexafluoride (720),and neodymium doped lanthanum magnesium nitrate hydrate (721) are probably of some appeal to chemists. Semiconductors (722-72n') have been more extensively examined than the cited references may suggest as has the acoustic NMR spectra of solids (716-720).
A N A L Y T I C A L C H E M I S T R Y , VOL. 46, N O . 5, A P R I L 1974
INSTRUMENTATION AND TECHNIQUE Thermometric detection of NMR has been described (721). Detection methods (722), optical detection of magnetic resonance wiggles (723),automatic sorting of signals in shift reagent spectra (724),a pulsed spectrometer with phase detection (72.57, a tunable spectrometer for very high frequency ranges (726),high resolving power in NMR ( 7 2 7 , a sensitivity test for spectrometers (728),and an inexpensive method for obtaining deuterium NMR on the XL-100 spectrometer (729) are among the interesting instrumental techniques that have been reported. Other articles have described detection of NMR a t low temperatures using a superconductive quantum interference device (730),instrumentation and application of NMR in a strong field (731), instrumental techniques demonstrated by analysis of a reaction mixture (732), difference frequency spectroscopy with analog Fourier analyzer (733), modification of the Varian HR-60 NMR spectrometer probe for operation a t very low temperatures ( 7 3 4 , detection of S M R using a Josephson-junction magnetometer 1735). and a w a r a t u s for the measurement of PMR sDectra under angle idtation (736). Experiments have illustrated NMR a t 310 MHz with a suDerconductine solenoid (737). NMR flowmeter techniques (738), transverse-magnetization recovery in the rotating frame (739),stopped-flow NMR spectroscopy (740), microtechniques of paramagnetic moment measurements (741). determination of magnetic susceptibilities by new NMR method (742, 743), and a digital pulse generator for NMR experiments (744). A sample container for radioactive materials ( 7 4 4 , a cross-coil probe for high-sensitivity low-temperature measurements (746), combined gas chromatography and NMR techniques (747), and methods of determination of purity in organic compounds (748) have also been presented. Residual splittings in off-resonance decoupled NMR spectra 1749), multiple field modulation (750),a low temperature uhf NMR system (7*51),a tunnel diode NMR spectrometer (752), an automatic low-field spectrometer (7,5.S),and modifications for observing a variety of nuclei (754) have been described. An automatic laboratory flood control system for the Varian A-60 (755) and a useful method for sealing glass tubing in a dry box (756) have been reported. COMPUTER APPLICATIONS Computer techniques for NMR spectra have included data processing of spectra with a PDP-8/1 computer (757), use of an on-line digital computer for enhancement and integration of spectra (7,58),applications of computers for structure elucidation of organic compounds (759),a computer program for plotting NMR spectra (760),computerized system for storing, retrieving, and correlating NMR data (761. 762), telephone directory format for NMR spectra retrieval (763),and specialized computer apparatus in radiospectroscopy of biological materials (764). Other applications of computer techniques to NMR studies have included a computerized KNIR system for polarized targets (765), data processing of instrumental analysis by small computer (766). a computer program for analysis of small-sized compounds (767), computer-aided approach for analysis of the NMR of histones (768), NMR spectrometer using a superconducting magnet and digital data processing (769),and pulsed single resonance spectra calculated with an analog computer (770). Computers have been utilized in the calculation of trial parameters for an AA’BB’ system (771), calculation of spectra in response to pulsed irradiation (772), and quantum mechanical calculations (773). A general discussion of the use of a computer in NMR spectrometry (774) has also been presented. LINE SHAPES AND BROADENING The line width method for determining chemical exchange rates from NMR spectra with some simplification has been applied to a number of chemical systems (775). Line shapes for the AB + CD AC + BD system (776), total line shape analysis (777), and computer handling of
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the two-site exchange problem (778) have been ’described. The effect of dislocation broadening on the NMR line shapes of solids (779), line shapes for various solids (780783), critical behavior of the autocorrelation function in NMR line narrowing (784),and line parameters of adsorption and dispersion Lorentzian curves under conditions of combined modulation and saturation distortion (785) have been evaluated, as has the theory of NMR detected by nuclear radiations (786) and line shapes for spin systems containing several quadrupolar nuclei (787).
CHEMICAL EXCHANGE Complete NMR line-shape fitting for exchange reactions in solution (788) and NMR line shapes of ammonium ions undergoing quantum mechanical tunneling (789) have been evaluated theoretically. Application of a multi-site chemical exchange formulation of the Bloch equations to intramolecular and intermolecular processes (790), conformational exchange processes in molecular adducts of antimony pentachloride and N,N’-alkylureas (791), reversible 1,2-shifts of the ethyl group in 9-ethyl9,lO-dimethylphenanthrenonium ion (79.27, halogen exchange in binary mixtures of dimethyltin dihalides (793), a nitrogen-14 NMR study of acetonitrile in hexakisacetonitrileiron(I1) (794), and proton exchange reactions of hexammineruthenium(II1) (785), hydroperoxide groups with methanol (796, 7 9 7 , 2,4,6-trimethylpyrylium salts in deuterium oxide (798), oxadiazoles in trifluoroacetic acid (799), ammonium ions in weakly acidic nitric acid solutions (800), the urea-tert-butanol system (801), aliphatic oximes (802), methanolic formate buffer (803), and Nmethylacetamide in aqueous electrolyte solutions (804) have been described. Studies related to those cited here can be found in the section on conformational analysis. NMR SHIFT REAGENTS In view of the books (18-20), reviews (87-94), and theses (175, 178) mentioned earlier, only a few articles, which may have been overlooked in previous surveys, are considered here. Eu(DPM)3 (DPM = dipivaloylmethane anion) is probably the lanthanide shift reagent finding the most application. Eu(DPM)3 has been employed for the simplification of spectra of dibenzylidene fructose (805),fat-soluble vitamin acetates (806), a-phenyl-a,N-dimethylnitrones (807), propyl amine and neopentanol (808), 2-alkoxytetrahydropyran (809), acetyl alcohols derived from tetrahydropyran (810), sulfoxides (811), metallocenes (812), alkyl phenols (813), vinylogous N.N-dimethylformamides (814), amitriptyline metabolites (815), triterpenoids (816), adamantane derivatives (817, 818), cis-trans isomeric trisubstituted allylic alcohols (819) and N-alkylideneanilines (820). The sign and magnitude of induced PMR shifts (821) as well as the reaction of N-bromosuccinimide with methyl enol ethers of cyclohexane-1,3-diones (822) have been examined. Eu(fod)s (fod = 1,1.1,2,2,3,3heptafluoro-7,7-dimethyloctane-4,6-dionato) induced shifts of alcohols, ketones, amines, and nitriles (823). POly(methyi vinyl ether) (824), lipid derivatives (825), and 5,5-dimethyl-1,3,2-dioxaphosphorinan-2-ones (826) have been described. Allenic enantiomers (827) and the absolute configuration of a-amino acids (828) have been investigated using tris[3-(tert-butylhydroxymethylene)3-camphorato]europium(III) and bis[3-(trifluoromethylhydroxymethylene)-3-camphorato], respectively. The acetylacetone complex of ytterbium(II1) has been found (829) to have some uses as a shift reagent. NMR studies of rare earth complexes of 1,lO-phenantholine (830) and acetates and chloroacetates (831) as well as studies of the effects of lanthanide ions on lecithin membranes (832. 833), indicate that despite the vast amount of work with shift reagents since 1969, the applications of shift reagents to chemical problems is far from exhausted. Numerous applications of lanthanide shift reagents to polymer problems have been described (834-843). Aggregation (844) and gas chromatography studies (845) of lanthanide shift reagents have been reported. The tetraphenylborate ion has been employed (846) as a shift reagent for pyridinum ions.
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HYDROGEN BONDING, SELF-ASSOCIATION, ION PAIRS, ELECTROLYTE SOLUTIONS, AND SOLVENT EFFECTS Although effects of hydrogen bonding on NMR spectra are rather ubiquitous, study of hydrogen bonding in 3-cyclohexenylcarboxylic acid ( 8 4 7 , water dimer in waterchloroform solutions (848), benzamidoximes (849), polycrystalline hydrazinium hydrogen oxalate (850), and hydrogen bonding abilities of quinuclidine (851), heterocyclic N-oxides (8521, and CH groups of halogenated hydrocarbons (853) by NMR spectrometry have been reported, A variety of linear correlations between spectrometric parameters have been found for 4-nitroaniline and N,N-diethyl-4-nitroaniline (854). The intramolecular hydrogen bond in salicylaldehyde has been examined by NMR in a nematic phase (855). Self-diffusion coefficients and rotational correlation times for a variety of polar liquids,-e.g., methanol (856)-and self-association of water in propylene carbonate (857, carboxylic acids in inert solvents (858-860), and ethyl and methyl alcohols in benzene (861) have been investigated. The self-association of several other compounds is cited in other sections of this review. The structure of ion pair solvation complexes (862),ion pairing of amidinium salts in dimethyl sulfoxide (863), and ion pairs of the indene carbanion with alkali metal cations (864) in ether solvents have been discussed. PMR spectra of several unsymmetrically substituted quaternary ammonium cations ion paired with paramagnetic tetrabromocobaltate(I1) anions have been examined in dichloromethane solution (865). NMR studies of alkali metal and quaternary ammonium trifluoroacetates in trifluoroacetic acid indicate the formation of the hydrogen bis(trifluoroacetate) anion (866). A variety of ions have been shown t o interact significantly with acetonitrile, sulfolane, and dimethylsulfoxide (867). In concentrated acid solutions, triphenylcarbonium ions have been shown to interact with the perchlorate anion-experimental chemical shifts agreed with those calculated assuming -6 A separation between the perchlorate anion and the charged carbon atom (868). PMR shifts induced by cations and anions in aqueous (869), methanol (870), and water-methano1 solutions (871, 872) have been described. The NMR spectra of complex ions in molten salt mixtures has been reviewed (873). Solvent effects on the NMR spectra of gases and liquids have been treated theoretically (874). Solvent effect studies have been reported for water in organic solvents (875), borane adducts in benzene and hexafluorobenzene (876), cyclopropanols in pyridine (877), trimethylcarbinol (878), 3-hydroxy-3-methylbutyrolactone (879), benzaldehyde (880), tetra-substituted ethanes (881), 1,4,7,7-tetrachloro2,2,3,3-tetradeuterionorbornane(882), 2,2’-dihalodiethylethers (883), nonaromatic heterocycles (884), and polar compounds containing acidic hydrogens (885). BIOCHEMICAL SYSTEMS The vast number of NMR studies of compounds of biochemical interest reflects not only the challenge and significance of the problems and the power of NMR techniques but also the research funding devoted to such investigations. Muscle systems (886-888), sciatic nerves (889, 890), self-interaction of chlorophyll-a (891), hemin and hemoglobin systems (892-905), cytochromes (906-908) membranes (909-919), lipid bilayers (920, 921), and related micellar solutions (922, 923) have been examined. Chlorine-35 NMR studies of dodecyl sulfate binding to bovine serum albumin (924) and of the active site zinc of horse liver alcohol dehydrogenase (925), a thallium-205 NMR study of pyruvate kinase and its substrates (926), and the use of lanthanide cations as probes in biological systems (927) have been reported as have studies of guanine-uracil base pairing (928), interaction of ethidium bromide with uracil residues (929),interactions of tyrosine and tyramine with nucleic acids and their components (930), flavine adenine dinucleotide (931), NMR titration curves of histidine ring protons (932, 933), biologically important acridine-type heterocycles (934), histidine-containing cross-links from collagen (935), intermolecular nuclear shielding due to aromatic amino acids of proteins 318R
and prophyrins (936),hindered rotation in methyl N-acetylsarcosinate (937), hydroxy amino acids (938), dipeptides of asparagine, aspartic acid, phenylalanine, and tyrosine (939), as well as various other peptides (940-950), ribonuclease (952-955), and nucleosides and nucleotides (956-959). Transaldimation and its role in the mechanism of vitamin Be enzymes (960), indole NH resonances of lysozyme (961), interaction of various substrates with enzymes (962-972) and 0-lactoglobulin A (973), the tumor inhibitors eupaserrin and deacetyleupaserrin (974), selfassociation of benzylpenicillin in aqueous solution (975), the structure of kromin (976), gramicidin A‘ (977), bikaverin and norbikaverin (978), pestalotin (979), gibbane derivatives (980), phaseollidin (981), cryptosporin (982), melatonin (983), concanavalin A (984), viomysin (985), corticotropins (986), actinomycin D ( 9 8 3 , catechol estrogens (988), insulin (989), and lysine vasopressin (990-992) have been examined. NMR spectrometry has been used to study rotamer populations of amphetamines (993), 3-C(dimeth0xy)phosphinyl derivatives of D-glucose, D-allose, and D-ribose (994), trimethylsilyl derivatives of flavonoids (995), @-methyl derivatives of arabinosylcytosine (996), glycosylamines containing the indole nucleus (997), methyl ethers of dissacharides (998), manganese binding by fructose phosphates (999),methyl ethers of D-galactopyranose and its derivatives (1000-1002), ~-aldgarose(1003), hydroxyachillin (1004)and coleon E (1005). Artifacts produced by chloroform and methylene chloride during the extraction of amines and alkaloids (1006) and studies of ternary complexes of adrenaline, adenine nucleotides and cobalt(II), and magnesium ions (1007) have been reported. Of analytical significance are the determinations of sodium cacodylate injections (1008), aminophylline in tablets (1009), trimethadione in various dosage forms ( I O I O ) , pentylenetetrazol in tablets and injectables ( l o l l ) , and 2,5-dimethoxyamphetamine (1012) by NMR.
GENERAL ORGANIC NMR spectra have been utilized in studies of the origin of anisochronism of geminal groups in conformationally mobile systems (1013), determination of the acid or base content of organic compounds (1014), molecular motion. (1015), some derivatives of squaric acid (1016), the preferential solvation of hydrogen peroxide and water (10171, tetraphenylethylene (1018), cyclopropyl derivatives (1019), bromopentachlorocyclohexanes and bromotrichlorocyclohexenes (1020),the radical anion and dianion of [16]annulene (1021), some chroman derivatives (1022), the bicyclo[2.l.l]hexyl cation (1023), dianion [12]annulene (1024), hexachlorocyclopentadiene adducts of 1,3-alkadienes (1025), polydeoxyriboadenylic acid (2026), isocoproporphyrin (1023, and trifluoroethanol (1028). Investigations on butane (1029), hydrogen bonding and long range coupling in protonated haloacetones (1030), magnetic shielding in the water molecule (1031), donor groups in polydentate ligands (I032), keto-enol equilibrium of 3hydroxy-2,4-dimethylcyclobutenone(1033), magnetic nonequivalence of geminal allenic protons (1034), protonated cyclopropane intermediates (IUY5), mechanism of the benzidine and Wallach rearrangements (1036), directions of dipole moments of aromatic heterocyclopentadienes (1037, and determination of the angle $ in peptides (1038) have been reported. Other articles have examined the functional form of the Karplus equation (1039), the validity of approximate equations Kc in dynamic NMR (1040), the carbon-14 spectrum of pentafluorobutane (1041),first-order spectra from alicyclic and aliphatic hydrocarbons (1042), feasibility of determining the optical purity of ketones (1043), spectra of rapidly-rotated solids containing reorienting molecular groups (1044) and the 220-MHz spectra of mesoporphyrin IX dimethyl ester, deuteroporphyrin IX dimethyl ester, and protoporphyrin IX dimethyl ester (1045). Chemical shift data have been tabulated for monosubstituted benzenes (1046),benzoic and toluic acids (1047), several 0-disubstituted benzenes (1048), 1-substituted naphthalenes (1049), nonplanar condensed benzenoid hydrocarbons (1050), trifluoromethyl-substituted naphthalene derivatives (1051), 8,8’-substituted-l,l’-binaphthyls
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aminomethy1)ferrocene (1108), wideline NMR studies of fluxional organometallic molecules in the solid state (1109), molecular motion in solid trimethylaminegallane (I 1I O ) , conformational studies of bridging carboxylate complexes of palladium(I1) and platinum(I1) ( I 1 I I ) , conformational effects in platinum complexes of methylglycines (1112), and studies of rotational isomers of 2-furanaldehyde (1113) have been reported. Keto-enol tautomerism (1114), tautomerism of nitrogen containing cyclic and acyclic compounds (11 1 5 ) , and geometrical isomerism of P-diketonate complexes (1116) have been the subjects of extensive reviews. Studies have been made of the tautomerism of 2-phenylbutyric acid anhydride (1117), rotational barriers in highly substituted diphenyl ethers (1118), and the barrier to pyramidal inversion of diisopropyl-p-tolylstibine ( 1119), as have studies of conformations of ortho-substituted diphenyl ethers and thioethers (1120), 2-acetylfurans (1121), a # unsaturated cyclohexenone derivatives (1122), 2-formylthiophenes and furans (lZ23), ring inversion 2-halomethyl-1,3-dioxanes (1124), and 1,4-dioxane (1125), and configurations of enamines (2126-1128). Rotational isomerism of trifluoroacetones (1129), 1,l-bis(dimethy1amino)ethylenes (1130), hindered rotation in carbamates (1131), aryl isopropyl ketones and aryl benzyl ketones (1132), protonated a-haloacetophenones (1133), and protonated benzaldehydes (1134), conformational studies of cyclic amine oxides (1135), piperidines (1 Z36), alkyl and aryl carbonates (1137), diphenyl ethers (1138), monothiocarbonates ( I 139), succinic and methylsuccinic acids (1140), 1,3-dioxanes, (1142, 1I42), cyclohexaneformaldehyde (1143), tautomerism of 2-amino-2-oxazolin-4-ones (1144),alkyl substituted P-diketones (1145, 1246), and aliphatic acyldiacetylmethanes (1 147) have been reported. NMR spectrometry has been employed to elucidate conformations of metal-free ferricrocin and ferrichrysin (1148), various hemoglobins ( I 149), proteins ( I 150), cyclic pentapeptides (1151), nucleosides (I152), oxytocin (1153, 1154), lecithin in vesicles (1155), poly(L-alanine) (1156), poly(hydroxy-L-proline) (1157), and pyranoid sugar derivatives (1158). Of particular interest are some studies of antihistimines (1159), dimethoxyamphetamines (1160), acetylcholine and related compounds (1261-1 164) and nicotine (1161). The low barrier of inversion of tetraphenylene (I165), chirality of triarylmethyl cations (1166), ring rotation in [2.2]metaparacyclophane (1167),hindered rotation in tertbutyl groups (1168), styryl cations (1169), acyclic hydrocarbons (1170) and 1,1,2,2-tetrachloropropane( I 17I), conformational studies of 1,2,3-tribromopropane ( I I 72), nbutane (1173), 1-butene (1174), straight chain hydrocarbons (1175), polyethylene (11 76), 0-substituted 1,l-diphenylethanes (1177), compounds with secondary methyl CONFORMATIONAL ANALYSIS, TAUTOMERISM, groups (1178) cyclohexene (1179), highly substituted cyAND ROTATIONAL ISOMERS clohexenes (1180), bridged cyclobutanes ( I 181), dimethylThe empirical correlation of NMR chemical shifts and cycloheptanes (1182), cyclopentanes, cyclopentenes, and conformations in ethers and amines has been described cyclopentene oxides (1183), dibenzocycloocta-1,5-diene (1092) as has the effect of internal rotation on NMR relax(1184), monosubstituted alkyl-benzenes (I 185), neopentylation times for macromolecules (1093), a study of stereobenzenes (1186), polyacenes ( I1 8 7 , benzohexahelicenes chemically nonrigid tricarbonyl-1,2-bis(dimethylphosphi- (1188), meso- and ra~-2,2’-bis(hexahelicyl)(1189) have noethane)iron(O) ( 1 0 9 4 , conformational dependence of been reported. A method for assigning dihedral angles to vicinal H-N-C-H coupling constants in peptides (1095),a hydrocarbons adjacent to a methylene groups using comtheoretical study of long-range H-H coupling constants puter analyzed NMR coupling constants in a modified across a dual homoallylic and HC-X-CH path in fiveKarplus equation has been presented ( I 190). The analysis membered rings (1096, 1097) and an attempt a t automatof mixtures of isomeric polynuclear hydrocarbons by NMR ed structure analysis of organic compounds using NMR can employ methyl shifts and peak multiplicity informa(1098). Strain energy minimization calculations for bicytion (1191). clo[3.l.l]heptane gives good agreement with enthalpy and Barriers to rotation about carbon-nitrogen bonds conentropy of activation values determined by NMR (1099). tinue to be of considerable interest as indicated by the Calculations of the shielding effect of a freely rotating plethora of studies (1192-1221) of amides and thioamides. magnetically anisotropic group (1100) and chemical shifts Conformational studies have been reported for a variety of in hydrocarbons (2101) have been presented. Cross-ring sulfur compounds: 1,3-dithiolanes (1212), trimethylene couplings for stereochemical assignments for four-memsulfites (I213), bithienyl derivatives (1214, 1215), chlorobered rings (1102), conformation determination in parasulfides (1216), s-tetrathianes (1217 ) and bis(m-nitromagnetic metal complexes (1103), free rotation of coordipheny1)disulfide (1218). A number of oxocanes have been nated tetracyanoethylene ( 1104), hindered rotation of studied using 251-MHz PMR (1219). Internal rotation in coordinated phosphorus trifluoride (1105), torsional barbenzamidinium ions (1220) and nitroanilines (2221), inriers in ferrocenylcarbonium ions (Z106),conformations of version barriers in aziridines (1222, 1223) and conformaalcohol derivatives of tricarbonyl(diene)iron compounds tional studies of azetidine derivatives (1224), hexahydro(Zl07), temperature dependence of diastereotopic methytetrazines (1225), c-triazolines (1226), [7](3,5)-pyrazololene protons and methyl groups in 2-isopropyl-l-(dimethyf- phanes (Z227), N,N’-dialkyl-1,3-diazines(1228), acyclic
(1052), isomeric benzoxazoles (1053), fused benzo derivatives (1054), intramolecular 1,2-hydrogen shifts in difluoro- and dimethylbenzenium ions (1055), and polychlorinated biphenyls (1056). Chemical shift data have also been incorporated in the magnetic shielding of acetylenic protons in ethynylarenes ( 1 0 5 3 , effect of the hydrogen bond on the internal rotation of biphenyls (1058), determination of aromatic substitution patterns (1059), interpretation of proton and carbon-13 shifts in substituted benzenes (1060) and in the assessment of simple theories of chemical shifts of aromatic protons as applied to substituted naphthalenes (1061). Solvent effects on chemical shift have been discussed for benzene in amidoxines (Z062), the electronic character of substituted aromatic systems (1063), self-association of toluene (1064),benzene in methylbenzoic esters (1065), a novel approach to aromatic solvent-induced shift (1066), effects on the protpn internal chemical shifts of some meta-substituted nitrobenzenes (1067, aromatic solvent-induced shifts in monosubstituted benzenes (Z068), benzene dilution shifts and steric interactions in N,N-dialkylamides (1069), polar solutes in weakly associating aromatic solvents (Z070), benzene-induced solvent shifts a t high solute concentration (1071), and the role of the internal reference in aromatic solvent induced shifts (1072). NMR spectrometric .investigations have included studies of 1,3,5-trifluorobenzene and substituted fluorobenzenes containing free radicals (Z073),N,N-dimethylformamide-aromatic systems (Z074), intramolecular charge transfer in (dialky1amine)-nitrobiphenyls (1075), molecular motion of certain 1,3,5-trinitrobenzene complexes (1076), dimers from a-alkoxybenzyl radicals (1077), ring inversion in tetrabenzocyclooctatetraene (1078), hydrogen bonds in 0-s,ubstituted phenols (1079), charge-transfer complexes of 1,3,5-trinitrobenzene, picric acid and fluorani1 with methoxy- and methyl-substituted benzenes and biphenyls (ZOsO), and benzenium ion and monoalkylbenzenium ions (1081). A calculation of inter-ring proton couplings (1082), inter-ring coupling in l&dimethylnaphthalene (1083), and spectral parameters of disubstituted anilines (1084) have also been reported. Investigations on the complex layer of alkylbenzenealuminum chloride-hydrogen chloride (1085), the benzene nucleus as a probe for the 7r-electron structure of annulenes (Z086), interaction between dibenzacridines and benzene (1087), eometry of N-benzalaniline (1088), and the structure of k-benzalanilinium ions (1089) have been completed. The effects of electronic buttressing on the conformations of some 0-disubstituted benzenes (1090) and the rationalization of procedures for processing data obtained from NMR studies (1091)have been discussed.
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and cyclic tetraalkylhydrazines (1229, 1230), N-alkylpivinyl polymers (1289), phenanthrenes (1290, 1291), benperidine and morpholine N-oxides (1231), N,N’-dialkylzofluorenes (1292), branching in polyethylenes (1293) and hexahydropyrimidines (1232) and N-aminobic clo the keto-enol equilibrium of acetylacetone (2294).Investi[2.2.l]hept-5-ene-2,3-endo-dicarboximide (1233) have tee, gations utilizing high resolution NMR have also included reported. The conformations of l-anilinonaphthalene-8characterization of ion-exchange resins (1295), dihalogensulfonate have been studied (1234) by fluorescence and ated toluenes (1296), bifluoride ion and its homolog PMR spectrometry. The tautomeric structure of 1(I297), thermal decoupling in pentaborane (1298, 1299), methyl-5-(methylamino)tetrazolein deuterated dimethyldiborane and tetraborane studies (1300), allylic derivasulfoxide has been investigated and a caution regarding tives of Group IV B elements (1301) and base pairing in the use of deuterated dimethylsulfoxide reported (1235). four purified transfer RNA molecules (1302). High-resoluConformational studies of five-membered ring phosphates tion carbon-13 NMR spectra of monohalobenzenes (1303), and phosphites (1236), 2-dimethylamino-5-tert-butylpolyacrylonitrile (1304), and some polyelectrolytes (130,5) 1,3,2-dioxaphosphorinane(I237), a n adamantoid pentaoxhave been reported. High-resolution NMR evidence of yphosphorane (1238), 2-phospha-1,3,2-dioxaphospholane conformational preference a t a solid interface (1306) and and cis and trans isomers of 2-chloro-4,5-dimethyl-l,3,2- investigation of the structure of the adducts formed by the dioxaphospholane (1240)have been described. interaction of benzylidenemalononitriles (1307) have apMetal ions encapsulated by three-dimensional macrocypeared. clic ligands (1241, 1242) conformations of tris(diamine) High-resolution NMR studies of relaxation involving chelates (1243-1245), stereochemistry and rearrangement band shape analysis for equilivalent nuclei (1308) and rates of some tris(p-thioketonate) chelates (1246),tris[( +) nonequivalent two-spin systems (1309), and selective re-3-acetylcamphorato]ruthenium(III) (1243, geometric isolaxation-time measurements (1310) have been discussed. mers of cobalt(111) (R)-N,N’-dimethylpropylenediamine The use of a high resolution KMR spectrometer for re(1248), isomers of bis(L -aspartato)cobaltate(III) (1249), cording solid-state phosphorous-31 spectra (1311), presand cis and trans tetraaminecobalt(II1) complexes (1250) sure dependence of proton chemical shifts (1312), deterhave been examined by NMR spectrometry. Modes of inmination of magnetic moments in solution (1313), meatramolecular rearrangement in octahedral complexes have surement of frequency separations using a frequency modbeen examined in detail (1251). ulated observing field (1314), and resolution enhancement of high resolution NMR spectra of polymers with the aid of a computer (1315) have been considered. The calculaPOLYMERS tion of response in high-resolution experiments (1.316) has also been described. Reviews of high resolution NMR spectrometry of polymers (1252) and problems of aromatic copolymer structure (1253) have appeared. The use of proton NMR and I3C GENERAL INORGANIC NMR in the determining the structure of linear polymers Molecular interaction theory has been employed (1317) and rubber (1254) has also been discussed. Articles deto calculate xenon-129 solvent shifts in various gases. Calscribing the NMR spectra of poly(viny1acetate) (1255), culated and experimental results were in good agreement. poly( 1-butene) (1256), polymerization of cyclic ethers Complexes of 1-(2-aminoethyl)aziridine (2318), polyami(1257, poly(y-methyl L-glutamate) solutions (1258), polynocarboxylate complexes of vanadium(V) (1319), sulfur (vinylchloride) (1259) poly-P-(a-isobutyl L-aspartate) bridged dinuclear complexes (I320),protonated ketones as (1260), methyl methacrylate-methacrylic acid copolymers NMR models for organotransition metal cations (1321), (1261), 1,2,3,4-tetrahydronaphthalenepolymer (1262), and titanium-47 and titanium-49 NMR of Ti(IV) halogen compoly[(2,5-dioxo-1,3-pyrrolidinediyl)dimethylene] (1263) pounds (1322),fluxional behavior of organotitanium comhave been reported. NMR investigations of vinyl chloridepounds (1323, 1324), titanocene (13253, and zirconocene isobutene copolymers (1264),mechanisms of epoxide poly(1325, 1326) derivatives with p-diketonates, alkoxy derivamerization (1265), poly(?-benzyl L-glutamate) in solution tives of x-cyclopentadienylzirconium(1V) ( 1 3 2 7 , seven(1266), oligomers derived from terephthaloyl chloride and coordinate Ti(1V) dithiocarbamates (1328), niobium-93 p-ciminobenzhydrazide (1263, copolymers of polypeptides NMR of niobium fluorides in hydrogen peroxide solutions (1268), structure of oligomeric polybutadienyllithium and (1329), NMR of addition compounds of niobiumW) and polybutadiene (1269), and poly(viny1 alcohol) (1270) have tantalum(V) (1330-1332), isonitrile Cr(0) and Mo(0) comappeared. Other studies have included NMR and optical pounds (1333),bonding isomerism of zero-valent Group VI notatory dispersion of L-alanine blocks flanked by benzyl B benzazole complexes (1334), substituent effects in aniL-glutamate, benzyl L -aspartate and N-carbobenzoxy-Lline (1335) and alkylbenzoic acid (1336),chromium tricarlysine (I271), helix-coil transitions in poly(? -benzyl D A bonyls, inter-ring movement in fluorene (13.39, and correglutamates (1272), characterization of the host polymers lations of carbon-13 chemical shifts with Cotton-Kraihanand application of the host-guest technique to random zel force constants (1338) of chromium tricarbonyl compoly ( hydrox ypropylglutamine-cohydroxybutylglutamine plexes have been described. Intramolecular carbonyl (I273), a low-molecular weight poly(trans-2-methylpentascrambling (1339) in molybdenum complexes, stereodieny1)lithium compound (1274), cationic polymerization chemically nonrigid molybdenum compounds (I.Y40-1.143), of 6,8-dioxabicyclo[3.2.l]octane(1275), nuclear magnetic ligand derivatives of tricarbonyla-cyclopentadienylmolrelaxation in poly(tetrafluoroethy1ene) fibers (1276), and ybdenum bonded to dimethyl- and trimethyltin (1344), the effects of molecular motion on the second and fourth correlation between infrared stretching frequencies and moments of drawn poly(oxymethy1ene) (1277). Variable carbon-13 chemical shifts of x -cyclopentadienyliron cartemperature studies such as the NMR absorption of pobonyls (1344, and manganese45 NMR studies of a numly(tetrafluoroethy1ene) ?-irradiated a t high temperature ber of carbonyl complexes (1346-1348) have been re(1278), paraffin deposits produced a t low temperatures ported. An experiment has been presented (1339) which is (1279), and the tunnel effect of methyl groups in high useful for teaching some techniques of organometallic synpolymers a t very low temperatures (1280) have been exthesis and use of NMR spectrometry. NMR studies have hibited. The determination of the degree of polymerizabeen reported for some Group VI11 polypyridine complexes tion of a polymeric amine from NMR data using a least(1350), cis-dihalotetrapyridineruthenium(I1) compounds squares approach (1281)has also been discussed. (1351),pentaamineruthenium species (1352-1354), anionic Ru(I1) anionic complexes (1355), and stereochemically HIGH-RESOLUTION NMR nonrigid ruthenium compounds (1356, 13.57). Several alkylcobaloxime dimers (1358), intramolecular rearrangeA review of the applications of high-resolution proton magnetic resonance spectrometry (1282) has been presentment reactions of tris(/3-diketonato)metal(III,IV) complexes (1359), the unusual temperature dependence of ed. High resolving power NMR (1283) has also been dissome diamagnetic dialkyldithiocarbamate chelates ( 136O), cussed. High-resolution NMR has been applied to studies mixed complexes of cobalt(II1) with 1,lO-phenanthroline of proteins (1284), intermolecular relaxation processes and ethylenediamine (13611, Rh(II1) and Ir(II1) hydride (1285), polysulfones of monolefins (1286), the electronic complexes (1362) and Rh(I), Rh(II), and Rh(II1) comstructure of vinyl monomers (1287), complexation of vinyl chloride by tetrahydrofuran and butyraldehyde (I288), plexes with tert-butylphosphines (1363). have been inves320R
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tigated by NMR. Oxygen-17 NMR studies of iridium and rhodium molecular oxygen compounds (1364) have been reported as have studies of the photoproduct of rhodium(111)-D( - ) -1,2-propylenediaminetetraacetate(1365), phosphine exchange in rhodium(1) fluorophosphine derivatives (1367), cationic oxygen adducts from rhodium and iridium carbonyl salts (1368), and stereochemical nonrigidity in rhodium(1) phosphite cations (1369). The NMR spectra of halo(alkene)iridium(I) complexes (1370), and iridium hydride complexes (1370-1372) have been reported as have studies of ligand-exchange equilibria of [alkyl(fluorocarbon)phosphine]nickel carbonyls (1373), trin-butylphosphine- -cyclopentadienylnickel mercaptides (1374), and zinc(I1) dithiotropolonates (1375). NMR of mixtures of bis(N-methylsalicylaldiminato)nickel(II) and the corresponding zinc compound indicate a rapid ligand exchange involving paramagnetic mixed-metal oligomers (1376). DEUTERIUM NMR investigations of deuterium systems include toluene, toluene-cu-d3, and toluene-do (1377), deuterium isotopic effect in carbon-13 NMR (1378), deuteron quadrupole couplings in deuterated glycine (1379), proton and deuterium spectra of ethyl bromide (1380), deuterium isotope effects on carbon-13 chemical shifts in benzene and substituted benzenes (1381), PMR and deuteron magnetic resonance studies of 1,5-diphenylverdazyls (1382), and specifically deuterated cyclohexane compounds (1383). NMR spectra were utilized in a study of the preparation of deuterated proteins and enzymes (1384). the monooctanoin-deuterium oxide system (1385), boron deuterides (2386), and the study of potassium deuterium bis(triflu0roacetate) (1387). Nuclear magnetic double resonance studies of the effect of deuterium substitution upon 1J(31P-1H) (1389). deuteron relaxation in paramagnetic solutions (1390), deuteron magnetic resonance of bis(n-cyclopentadieny1)dideuteriomolybdenum and bis(n,-cyclopentadieny1)dideuteriotungsten (1391j, and comparison of proton and deuteron NMR of some paramagnetic transition metal complexes (1392) have been reported. Deuterium isotope effects observed in NMR shifts induced by lanthanide complexes (1393) and NMR determination of some deuterium quadrupole coupling constants in nematic solutions (1394) have also been discussed.
HELIUM A review of NMR in helium-3 (1395) has been presented. Nuclear relaxation of gaseous helium-3 on surfaces (2396) and zeolite (1397), magnetic field dependence of relaxation times in solid helium-3 (1398), and NMR study of the formation and structure of an adsorbed helium-3 monolayer (2399) have been described. The displacement of the NMR line of helium-3 by metastable exchange collisions (1400), liquid helium-3 (1401), and its solidification curve (1402) a t very low temperatures were discussed. NMR studies of protons and helium-3 contained in gold films (1403) have also been reported.
ALKALI AND ALKALINE METALS Lithium-7 NMR has been utilized in the study of the interaction of lithium ion with pentamethylenetetrazole (1404), investigation of the structure of some aromatic ion pairs (1405), and structure and ring currents in some aromatic dianion systems (1406). Proton NMR investigations of the effects of lithium chloride on the proton chemical shifts of diglyme and triglyme in aqueous solution (1407), molecular motion and structure around the hydrated ions Li- and A13+ (1408), and NMR study of carbon-lithium bonding in arylmethyllithiums (1409) have been made. Sodium-23 NMR studies in mixed solvents 11410), of solvation shell changes from the linewidth (1411), solvation of sodium ions in nonaqueous solvents (1412), quadrupolar broadening (1413), and of sodium ion interactions (1414) have been reported. Sodium magnetic resonance in basic solvents (1415), the effect of water on the sodium-23 quadrupole interaction (24161, and sodium-23 NMR of sodium dibenzo-18-crown-6 in N,N-dimethylformamide (1417) have been described.
An investigation of cation-anion interactions by potassium-39 NMR (1418) has been presented. Nuclear magnetic relaxation of rubidium-85 in some aqueous soap solutions (1419) and an atomic reference scale for chemical shifts of rubidium (1420) have been described. Evidence from cesium-133 NMR concerning complexation of cesium ion with ferric halides in aqueous solution (1422) and a superconducting solenoid field monitoring with cesium133 NMR (1422) have been discussed. NMR spectra of crystalline and glassy beryllium (1423), beryllium oxyacetates (1424), tetramethylammoniumthiocyanatobis(diethylberyl1ate) (1425), and bis(thenoy1trifluoroacetonato)beryllium (1426) have been exhibited. NMR of magnesium(I1) compounds have included studies of the mechanism of metal ion promoted hydrogen exchange reactions (1427), formation and stereospecificity of vinylic organomagnesium reactions (1428), exchange studies with sparteine (14291, and magnesium-25 NMR in aqueous phosphate solutions (1430). Evidence for a guanosine-calcium(I1) complex (1431) has been provided by NMR spectra. Alkali metal NMR studies of radical anion solutions (1432), NMR properties of lunar samples (1433), complexing of sugars with metal ions (1434), and NMR studies of interaction between pyrimidine nucleoside and divalent metal ions in dimethyl sulfoxide (1435) have also been presented.
BORON Boron-11 spectra have been utilized in structural and conformational studies of the Bl~)H14~ion (1436), several dioxy- and diazaboracycloalkanes (1437), B-substituted borazines (1438), and aminoborane derivatives (1439). Variable temperature studies of B11H11~ and BllH7Br42- (1440), and hexaboranes (1441) have also been reported. Boron hydride spectra were recorded for the tridecahydrodecaborate(1 - ) ion (1442). pentaborane and phenylboronic acid (1443), and hexaboranes (1444). Boron-11-hydrogen coupling constants have been determined for vinyl compounds of boron (1445), polyborate ions in solution (1446), and some organoboron compounds (1447). Other organoboron compounds studied include cyclopentadienylboric acid esters (1448), w-dialkylaminoalkylboron compounds (1449), potassium tetraarylborates (1450), boron alkenyl compounds (1451), as well as octaborane and a few of its derivatives (1452). Deuteration and spectrometric studies of undecaborane derivatives were also reported (1453). Bonding studies of boron compounds with Group IV elements (1454), mixed boron trihalides (1455), substituted diboranes (1456), tetrahaloborate ions (1457) and difluoroborane complexes (1458) were also reported. B-Amino borazines (1459), tetra-n-butyl ammonium salts of B5H8and B6H9- (1460), and the Lewis basicity of 2-methylaminoborazine (1461) have also been investigated. Boron-11-phosphorous-31 NMR spectra were given for six-membered boron-phosphorus rings (1462) and complexes formed by borane with alkoxychlorophosphines (1463). Phosphorous-boron coupling constants as a qualitative measure of dative bond strength were also discussed (1464, 2463’). Fluorine-19 spectra were included in studies made on tetrafluorodiphosphine-bis(borane(3)) ( * ? I ) , and difluorophosphine-borane (1467). The NMR of AlB2 a t Darameters for boron-11 300 “K yielded auadruDole couDlinp. . and aluminum-57 (1468). Boron-11-NMR studies in lithium tetrahvdroboratealuminum tetrahydroborate-diethyl ether and -tetrahydrofuran systems (1469) have been given, along with electrochemical studies of monocarbon carboranes (1470) and synthetic studies of p-silyl and p-germy1 carboranes (1471), ~ , , U ’ - S ~ H ~ ( C(1472) ~ B ~ and H ~ )6,9-bis(dialkylsul~ fido)dodecahydrodecaboranes with mercuric salts ( 2473). Boron-11 spectra were also obtained for various germanium borate glasses (2474), (3)-1,2-BgC~H12-and [(3)-1,2BgC2H1112Co- ions (1475), and for boron halides as reagents in inorganic syntheses (1476). Metal-boron-11 works include resonance studies of zirconium and hafnium tetrahydroborates (14771. four-, and five- and six-boron metallocarboranes (14781, transition -
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metal monoborides (1479), p-tetracarbonyliron-hexaborane (1480), and double resonance proton-[boron-111 spectra of 0 - , m-, and p-carboranes and some of their organotin derivatives (1481). Heteronuclear magnetic triple resonance (1482)studies were also made. Utilizing boron-11 NMR, the distribution of boron sites in glassy boron oxide (1483) was determined. New interpretations of the spectra obtained from glassy borates (1484) and strontium borate glasses (1485) have also been reported. Other interesting boron NMR studies have included nitrogen-boron spin-lattice relaxation (1486) and interference effects in relaxation in liquid boron-10B trifluoride (1487). High resolution studies (1488), partially relaxed Fourier transform (1489), and line narrowing applications (1490) have also been presented. A computer simulation of boron-11 NMR in polycrystalline boron trifluoride (1491) has been among the interesting techniques applied.
ALUMINUM-GALLIUM-INDIUM-THALLIUM Aluminum-27 NMR spectra have been observed for solvated species of Al(C104)3 (1492),sulfato complexes of the hexaaquoaluminum ion (14931, the hydrolysis and polymerization of the hexaaquaaluminum(II1) cation (1494, and equilibrium solutions of mixed bromochloroaluminate ions (1495). Proton magnetic resonance studies have been carried out on pentaalkyldialuminum alkali metal oxides and related complexes (1496),the cyclohexane-aluminum bromide system (1497), and exchange studies of methyl groups between hexamethyldialuminum and trimethylgallium (1498). Proton NMR have also been utilized in solvation studies of aluminum(II1) in n-propanol (1499) and aluminum(II1) in ethanol (1500). Stoichiometric and synthetic reports include mixed hydride-bridged complexes between diisobutylaluminum hydride and diisobutyl aluminum chloride (1501), cis- and trans-cydotris(p-methylamido)tris(dimethylaluminum) and related compounds (1502), reactions of tribenzylaluminum (1503), studies of Me2A1(RNCO)OMe (I504), interaction between organoaluminum compounds and ditertiary phosphines (1505), mechanisms of epoxide polymerization (1506), and temperature dependent studies between disobutylaluminum hydride and triisobutylaluminum (1507). Other Group I11 NMR spectra have been reported: aluminum and gallium trimeric dicyclopropylmetal ethylenimides (1508), internal exchange in Group I11 metalloborane derivatives (1509),carboranes containing gallium and indium cage heteroatoms (1510), methyl group exchanges in Lewis acid-base adducts of Group 111 trimethyl compounds (1511), and quinolinolato complexes of aluminum, gallium, and indium dialkyls (1512).The relation between structure and proton donor strength of octahedrally coordinated tris(3,5-diisopropylsalicylato)aluminum(III), -gallium(III), and -indium(III) (1513), and direct hydrogen-l and phosphorous-31 NMR cation solvation studies of Al(C104)3, Ga(C104)3, and In(C104)3, in water-acetoneDMSO and water-acetone-HMPA mixtures (1514) have also been noted. NMR spectra have been described for octaethylporphinatothallium(II1) (1515) and substituted cyclopentadienylthallium(1) compounds (1516). NMR relaxation rates of thallium(1)-205 with respect to complexing of molecular oxygen (I527 ) and thallium-205-proton spin-spin coupling constants in substituted arylthallium dichlorides (1518) have been reported. Ligand exchange studies with indium(II1) complexes of trifluoromethyl-P-diketonates (1519), indium(II1) tetraphenylporphine complexes (1520), and complex formation of indium halide solutions in wateracetone mixtures (1521)have been described. CARBON-13 Although most carbon-13 NMR studies deal with organic compounds and properly belong in the preceding sections, a number of such investigations omitted there are included here. A review (1522) of recent advances in carbon-13 NMR instrumental design and applications has been reported. Carbon-13 NMR chemical shift studies have described some carbon sp3 systems (1523), N methyl-4-piperidones (1524), anisotropy of acetylene (1525), and transition metal carbene complexes (1526). 322R
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Quantitative correlations of the carbon chemical shifts of acyclic alkenes (1527)have also been discussed. Carbon-13 spectra have been used in the conformational analysis of methyl-substituted cycloheptanes, cycloheptanols, and cycloheptanones (1528). Stereochemically nonrigid organometallic molecules (2529) have also been reported. Carbon-13 studies include the structure of allyl cations (1530), site of protonation in sulfoxides (15313, benzyl compounds (1532) investigations of pyridine, nicotinamide, their cations and related compounds (1533), and as a tool to study organic solvation shells (1534). Carbon-13 coupling constants have been described for some nitroxide radicals (1535), monosubstituted benzene derivatives (1536), and in geometrical effects in molecular orbital calculations of a model carbonium ion (1537). Other carbon-13 coupling to hydrogen in studies of weak intermolecular hydrogen bonds (1538), and in elucidating torsion angle in uridine and related structures (1539) have been exhibited. Carbon-13-germanium-73 (1540), boroncarbon-13 (1541),aluminum-27-carbon-13 (1542),and tincarbon-13 (1543) coupling constants have also been discussed. Contact shift studies have included carbon-13 contact shift and molecular orbital studies on the interaction between halogenated molecules and nitroxide radical (2544, 1545), shifts induced by hydrogen bonding with nitroxide radical (1546),protic molecules in the presence of the nitroxide radical (1547), diamagnetic solvent molecules (1548), azanaphthalenes (1549), conformational dependence in six-membered rings (1550), of the 1,l’-dimethylmetallocenes (1551), and shifts of alkenes induced by silver(1) (1552). Carbon-13 NMR spectra of organophosphorous compounds (1553), chromium pentacarbonyl carbenoid complexes (1554),a-complexes of transition metals (1555), cyclopentadienylmagnesium compounds in tetrahydrofuran (1556), representative organometallic r-propene complexes (1557), and carbene and isonitrile complexes of chromium and tungsten (1558) have been observed. Lanthanide-induced chemical shift inquires have involved complexation of lanthanide chelates with saturated amines and rz-butyl isocyanide (1559), and signal assignment by alternately pulsed NMR and lanthanide induced chemical shifts (1560). Other interesting carbon-13 investigations are comprised of temperature-dependent spectra of h5-cyclopentadienyl iron decarbonyl dimer (1561), shielding effects in metal-alkyl, metal-olefin, and metal-allyl bonds (15623, hyperfine shifts in low-spin iron(II1) prophyrin complexes (1563), effect of paramagnetic metal ions on proton decoupled 13C NMR intensitie; (2564),elimination of the Overhauser effect with an added paramagnetic species (1565), and chemical polarization of carbon-13 and nitrogen-15 nuclei in thermal decomposition reactions (1566). A NMR study of carbon-13 monoxide-enriched T cyclopentadienyl manganese tricarbonyl in a nematic solvent (1567) has been described. Techniques discussing relaxation times of carbon-13 and methods for sensitivity enhancement (1568)have also appeared. Biological studies utilizing carbon-13 S M R include a specific labeling approach to the study of histidine residues in proteins (1569), determination of the tautomeric form of the imidazole ring of L-histidine (1570), interaction of macrotetrolide antibiotics with sodium, potassium, rubidium, cesium, ammonium, and barium ions (1571), the spectrometry of oxytocin, related oligopeptides (1572), and spectral analysis of tetrahydrocannabinol and its isomers (1573).
SILICON, GERMANIUM, AND TIN Silicon-29 chemical shifts have been presented for trimethylsilyl esters of inorganic and organic acids (1574), organosilicon compounds (1575), methylsilyl carboxylates (1576), monomeric silicon compounds (1577), and some carbon functional organosilicon compounds (1578), Silicon-29 chemical shielding anisotropy in some organosilicon compounds (1579), linear correlations between Si-Si force constants in disilanes (1580), and nuclear Overhauser effects for phenylsilanes (1581)have been discussed. Proton-silicon NMR spectra have been reported in studies
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of the migration of the trimethylsilyl group in silylated acylamides (1582), and spectra of benzylsilanes and phenyldisilanes (1583). A correlation of Hammett u constants with NMR parameters for substituted phenylsilanes, phenylmethylsilanes, and phenyldimethylsilanes has been described (1584). Carbon-13 and silicon-29 NMR spectra of phenyl- and benzyl-substituted silanes (1585)have also been exhibited. Solvent studies include effects on shielding constants in tetramethylsilane and cyclohexane (1586) and effects on hydrogen-1, carbon-13, and silicon-29 resonances in tetramethylsilane (2587). Other silicon NMR have reported silicon-29 Fourier transform (1588) and structural investigations of oligomeric and polymeric siloxanes by high-resolution silicon-29 NMR (1589). Nuclear magnetic resonance spectra of phenoxysilanes and phenoxygermanes (1590), germanium(I1,IV) fluoride (l592), and bis(trimethylsily1)-, bis(trimethylgermy1)-, bis(trimethylstanny1)-, and (trimethylsily1)piopynylmercury (1592) have been reported. Germanium-73 NMR spectra have been obtained of germanium tetrahalides (1593) and other organogermanium compounds (1594). NMR was utilized in analysis of the d,-p, interaction in organic compounds of Group IV B elements (1595). Studies of organotin compounds using the Del Re method (1596) have been reported. Tin-119 heteronuclear double magnetic resonance has been used in investigations of the structure of some 1,3-difunctional tetraalkyldistannoxanes (1597) and in ethyltin derivatives (1598), while tin-119 chemical shifts in organotin carboxylates (1599) have also been discussed. NMR measurements have been taken for dimethylformamide solutions of tin(1V) chloride (1600),five- and sixcoordinate complex tin ions (160I), diorganotin(1V) Schiff base complexes (1602), and other tin(1V) complexes with bidentate Schiff bases (1603). NMR studies of some trimethyltin carbamates (1604), tin(1V) complexes with N,N-dialkyldithiocarbamic acids (l605), of chloro(N,Ndialky1dithiocarbamato)diorganostannanes (1606), and reactions of dibromoalkanes with dimethyltin bis(N,Ndimethylthioseleno and diselenocarbamates) and related compounds (1607) have been reported. Proton NMR of (d-p)T interactions in stannanes containing unsaturated systems (1608), benzyltin derivatives (1609, 1610), trimethyltin derivatives of some 4-substituted phenylsulfides (1611), bicyclic organotin compounds (1612), and tetraorganotins ( 2623) have been given. Investigations of trialkyltin acetates (1614), anionic tetrahalo(2,4-~entanedionato)stannate(IV) complexes (1615) and tetrakis(trifluor0methy1)tin (1616) have been reported. Spectrometric inquiries of dicyclopentadienyltin(I1) and its methylcyclopentadienyl analog (1617 ) , structure and reactions of some monoorganotin(1V) compounds (1618), bis(acety1acetone)ethylenediimine adducts of organotin(IV) halides (1619), exchange reactions in trimethyltin derivatives (1620), preparation and reaction of tin-nitrogen compounds (1621), and propargylic and allenic compounds of silicon, germanium, and tin with chiral centers in the asymmetric a-carbon (1622) have been conducted. Tin-Group I11 metal-metal bonded derivatives (1623),and inductive effects on benzene solvent shifts in PMR spectra of (acetylacetonato)organoantimony(V)and bis(acety1acetonatoorganotin(1V) compounds (1624) have also been discussed. Shielding constants of ‘19Sn nuclei (1625),of fluorine bonded to octahedral tin(1V) complexes (1626), and primary isotopic effects on the magnetic shielding of l17Sn and Il9Sn (1627) have been observed. Proton-llgSn coupling constants were determined from the spectrum of the stannyl ion (1628); tin-117-phosphorous, tin-119-phosphorous, and phosphorous-phosphorous coupling were obtained from spectra of tertiary phosphine complexes of stannic chloride (1629), and tin-117, tin-119-proton longrange coupling was determined from spectra of alkylhalostannanes (1630). Metal satellite spectra of tetracyclopropyltin, tetracyclopropyllead, and dicyclopropylmercury (1631) and symmetrical isomers of tetrafuryl- and tetrathienyltin (1632)have also been reported.
NITROGEN-14 Nitrogen-14 quadrupole resonance studies have been made for substituted pyrimidines (1633),some compounds
containing N-N bonds (1634), and from linewidths in some organic liquids (1635). Nitrogen-14 chemical shifts have been described for quaternary ammonium salts of enamino ketones (1636), azines (1637),five- and six-membered N-heterocycles (1638), aliphatic gem-dinitro compounds and their anions (1639), a few linear triatomic species (1640), and as a simple diagnostic method of amino function of organic compounds (1641). Additivity rules for shifts in azoles (1642) have been discussed. Nitrogen-14 NMR studies have included azides (1643), azoles and their benzo derivatives (1644), 1,5-disubstituted tetrazoles (1645), mono-substituted pyridines (1646), 0-substituted N-ethylpyridinium cations (2647), six-membered aromatic heterocycles (1648), and azo compounds and hyponitrite ion (1649). Proton-nitrogen-14 coupling were discussed for the pyridine-water system (1650), some N-alkylnitrilium salts (1651), and diethylmethylvinylammonium bromide (1652). Other nitrogen-14 NMR were recorded for simple aminoboranes (1653), aminosilanes (1654), organometallic azides (1655),and some diamagnetic metal and triphenyltin thiocyanates and potassium selenocyantes (1656).Carbon-13, nitrogen-14, nitrogen-15, and oxygen-17 NMR spectra were reported for nitropyrroles and nitroimidazoles (1657)and their charged species (1658).
NITROGEN-15 Nitrogen-15 natural abundance spectra of hydrazines (1659), amines (1660), and amino acid derivatives (1661) have been described. Nitrogen-15 NMR have also been discussed for the pyridine system (1662),methylamine hydrochlorides (1663), while solvent and temperature effects were included with the spectra reported for acetamide15N (1664). Nitrogen-15-proton coupling has been exhibited in aniline derivatives (1665), benzamides and benzonitriles (1666), aniline (1667), and ortho-substituted anilines (1668). Reports on azoheterocycles (1669), spin-lattice relaxation of nitrogen-15 in organic compounds (1670), and nuclear Overhauser effects (1671)have been made. Nitrogen-15 NMR have been used in conformational studies of heterocyclic o-quininediazides (1672), adducts of boron trifluoride and antimony pentachloride with 1,3dimethylurea (I673), and in stereochemical dependence of the sign and magnetitude of coupling constants on geornetry in nitrogen-X(E)- and (2)-aldimines (1674). The effect of paramagnetic species on nitrogen-15 NMR (1675) has been reported, while application of INDOR to a study of l5N-pyrrole (1676)was also made. PHOSPHORUS Quantitative analysis studies by phosphorus-31 NMR (1677), as well as a general review of the applications of phosphorus-31 NMR (1678) have been presented. Phosphorous-31 NMR chemical shifts studies include complexes such as diethylphenylphosphorates (1679), phosphorus tribromide (1680), quaternary phosphonium salts (1681), coordinated tertiary phosphines (1682) and elemental phosphorus in the gas phase (1683). Solvent dependences of chemical shifts have been given for tetraphosphorous trisulfide (I684), diastereoisomeric pyrophosphoramides (1685), and elemental phosphorus (1686, 1687). Proton-phosphorus-31 spectra have been reported for phosphanes (1688), alkylphosphoranes (1689), eight -coordinate molydenum-phosphorus (1690) systems, monodimethylaminophosphoryl halides (1691),and tris(dimethy1pheny1)phosphine complexes (1692).The signs and magnitudes of long-range proton-phosphorus-31 coupling constants have been determined for methyl-substituted trithienylphosphine derivatives (1693), Me3CPC12 and (Me3C2)PCl systems (1694),and biphosphines (1695). A proton nuclear magnetic resonance study of substituent effects on organophosphorus compounds (1696) has been presented. Other organophosphorus studies report the 2-oxo-1,3,2-dioxaphosphorinane system (1697), symmetrical organic compounds containing two phosphorus atoms (1698), vinyl phosphates (1699), an investigation of the bonding in fourth-group phenylphosphines ( I 700),and P,P’-dimethyl-P,P’di-tert-butyldiphosphine (1 701). Equi-
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librium investigations of methylphosphorus moieties (1702), the phenylphosphine-pentaphenylcyclopentaphosphine system (1703), the halogen exchange on trivalent phosphorus (1704), and heteroaryl-phosphorus compounds (1705) have been described. Articles have also appeared describing the proton-phosphorus-31 NMR spectra of ditertiaryphosphines ( I 706), phosphorus containing heterocycles ( I 707), tri-3-furylphosphine derivatives ( 1708), and cyclic derivatives of phosphorus oxyacids (1709). Spectra have been utilized in structural studies of 2-substituted 1,3,2-dioxyaphosphorinan-2-ones(1710), bicyclic dioxyphosphorane ( 171I ) , 2-phenyl- 1,3,2-dithiaphospholane (I712),tetraoxaspirophosphoranes (1713), and other phosphorus-containing heterocycles (1714). A few interesting phosphorus compounds described include sodium tris[ethyleneglycolato(2-)]phosphate(l-) (1715), l-phosphabicyclo[2.2.l]heptane 1-oxide (1716) and 1,l-difluoro-3,3-bis(trifluoromethyl)diphosphine-~-oxide (1717 ) . Phosphorus-sulfur compounds such as thioesters of phosphorus(V) (1718), thiophosphoric acid esters (1719), and phosphorus(V)-sulfur(V1) nitride chlorides ( 1 720) have been described. A heteronuclear double resonance study of difluorophosphine oxide, sulfide, and selenide (1721) has appeared. Phosphorus-31 NMR studies of adducts of phosphorus oxychloride (1722), oxygen-, sulfur-, and nitrogen-bridged diphosphorus tetrafluoride compounds ( I 723), and linear diphosphazenes ( I 724) have been reported. Phosphoruboron NMR studies of phosphine adducts of mixed boron trihalides ( I 725), temperature dependent NMR of tetrafluorodiphosphine-borane ( I 726) and the reaction of some difluorophosphines with borane ( 1 727) have been reported. Synthetic studies of phosphorus containing complexes such as bis(fluorophosphinothioy1)sulfides ( I 728), isomeric N-methyl-1,2,4,6,3,5-thio(VI)triazadiphosphorines (1729), linear and cyclic chlorophosphazenes ( I 730), and bis(trifluoromethy1)thiophosphinic acid ( I 731) have been discussed. Discussions of deuterium substitution (1 732), carbon-13-phosphorus-31 spectra of tertiary phosphines (1733), and carbon-13, silicon-29, phosphorus-31 (1734) have also been useful. The phosphorus-31 NMR of purified tRNA (1735) and the pyrophosphate backbone of pyridine coenzymes (1736)have been described. In the chemistry of phosphorus, phosphorus selenide iodides (1737), phosphorus-31-selenium-7’7 coupling ( 1 738), and organophosphorus selenides (1739) has been reported. Other articles include alkoxyphosphonium hexachloroantimonates (1740) and bonding properties of silyl-. germyl-, and stannylphosphines (1741). Metal-phosphorus compounds such as cyanophosphine complexes of nitrosyl cobaltcarbonyl ( 1 742), and phosphine and phosphite complexes of mercury(II), cadmium, and tin (1743) have been discussed. Solution-structural studies of metal-phosphine and -phosphite complexes (1744), coordination sites of some paramagnetic ions (1745), platinum complexes (1746), and cobalt-nickel complexes ( I 747) have also appeared. A mechanistic analysis for FeH2[P(OC2H3)3]4 (1748), data for some di-tertbutylphosphine transition metal complexes ( I 749) and tungsten-183-phosphorus-31 spin-spin coupling ( I 750), and temperature-dependent proton-phosphorus-31 NMR spectra of some iron and ruthenium dihydrides (1751) are among the interesting topics presented. Iridium triarylphosphite complexes (1752), tertiary phosphine complexes (1753), and complexes of the type mer-[MXsLs](M = rhodium or iridium) ( I 754) have also been reported.
phenylantimony(V) derivatives of haloacetic acids ( 1763), dihalodiaryl(acetylacetonato)antimony(V) compounds (1764) and (acetylacetonato)organoantimony(V) compounds (1765) have been discussed. NMR spectra of asymmetrical tertiary stibines ( I 766) and methyl and ethyl fluoride-antimony pentafluoride complexes ( I 767) have been reported. Articles describing nuclear relaxation and molecular mobility in crystalline complexes of antimony trihalides with anisole (1768) and interaction between some weak organic bases and hydrogen chlorideantimony pentachloride in 1,2-dichloroethane solution ( 1769) have appeared. Selenium-77 spectra of 2-substituted selenophenes (1770) have been exhibited. NMR studies have also been made of selenium chloride pentafluoride ( I 771), monoand disubstituted selenophenes ( I 772), selenosemicarbazides and related compounds ( I 773), some selenium-containing dimethyltrichalcogenocarbonates (1774). oriented selenophene in lyotropic mesophase ( I 775), 4,5-dihydro1,2,4-triazole-5-selones ( 1 776), dichloro- and dibromo(tetramethylthiourea)selenium(II)(I 777) and the reaction of trans-chlorohydridotetrakis(piperidine)iridium(III) with cyanate, thiocyanate, and selenocyanate ( I 778). NMR of selenium compounds have been included in studies of the thermochromism of organic diselenides ( I 779), axial preferences in selenanes (1780), substituent effects in diphenyldiselenides and of thermally induced rearrangements in dibenzyl diselenide (1’781), intramolecular hydrogen bonding in selenophene P-diketones ( I 782), atomic reorientation rates in liquid selenium and arsenic triselenide (1783) and correlations of PMR-shifts of monosubstituted selenophenes with reactivity parameters ( 1784). Temperature dependence studies of selenourea ( 1785) have also been made.
SULFUR
Sulfur-33 magnetic resonance spectra ( I 786) and pulsed NMR sulfur-33 investigations ( I 787) have been reported. High-resolution proton NMR studies of sulfur compounds include polynuclear heterocycles ( I 788, 1789), 4-methyl-, 4-phenyl-, and 4,6,6-trimethyltriethylene sulfite (1790), trimethylene sulfite (1791), and substituted ethylene sulfites (I 792). Proton chemical shifts have been discussed for thieno[2,3blthiophene and thieno[3,2-b]thiophene ( I 793), acenaphtho[l,2-b]- and -[1,2-c]thiophenes (1794), aralkylhydropolysulfides (1795), sulfines and meso- and (r)-bis(phenylsulfiny1)methane (1796, 1797) while solvent effects were also investigated with chemical shift studies of substituted sulfoxides ( I 798)and carbon disulfide ( I 799). Conformational analyses of sulfur complexes include the proton magnetic resonance of thiocarbamoyl compounds ( B O O ) , mesityl-substituted sulfines (1801), alkenesulfonic acids (I802), ethyl mercaptan (1803), and bis(amino)sulfides and -disulfides (1804). The 4J(H-H) couplings in some 1,3-oxathiolan-5-one derivatives (1805),and thietane sulfones (1806) have also been described. Long range shielding of bivalent sulfur dependence on molecular geometry factors (1807) has also been reported. The products of the reaction of N-benzoyl-P-arylserinates with thionyl chloride (2808) and tetrasulfur tetranitride with strained olefins (1809) have also been reported. Proton NMR of sulfur compounds also has included ethylene sulfites (1810), trimethylsulfonium iodide (1811), simply organic sulfones, sulfoxides, and thioethers (1812), isopropylmethylsulfide derivatives (I813), and ethylene episulfone (1814). Studies of the hydrogen bonding of alkylated ARSENIC-ANTIMONY-SELENIUM bases to dimethylsulfoxide (1815)and between chloroform and N,N-disubstituted amides and sulfoxides (1816) have Nuclear magnetic resonance spectra have been reported for cis and trans isomers of cu-phenyl-4,5-dimethyl-1,3,2-also appeared. dioxarsolane (1755) and 2-chloro-4,5-dimethyl-l,3,2-diox- Articles describing the NMR of other sulfur systems include aromatic heterocyclics (1817),chemistry of the sularsolane (1756), alkoxy-, alkylthio-, and (organose1eno)dialkylarsines (1757), 2-chloro-1,3,2-dithiarsenane(1758), fur-oxygen double bond (1818), sulfur heterocycles (1819), and dialkylaminodifluoroarsines ( 2 759). The dynamic sulfinamide derivatives (1820), and chlorosulfinyl comstereochemistry of pentacoordinated arsenes ( I 760) and pounds (1821). Double magnetic nonequilivalence in ringsubstituted arylmethylsulfites (1822) has been discussed carbomethoxymethylenetriphenylarsenanes ( I 761) have as well as solution studies of S-triazines (1823),substitutalso been presented. ed thioglycolic acids ( l 8 2 4 ) , thiotrithiazylchloride derivaAmong the organoantimony compounds reported, isomtives (1825), aromatic sulfines (1826). and monothioformic erism in hexacoordinate diphenyl- and 2,2’-biphenyleneacid (1827). Spectra of di-, tri-, tetra-, and hexa-coordiantimony(V) P-diketonates (17621, trimethyl- and tri324R
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nate sulfur substituents (1828), quinizarin-2-sulfonic acid (1829), tetramethyldiarsine disulfide (I830), sulfur containing ru-amino acids (1831), and sulfur ylides (1832) have also been examined. Proton spectra for complexes with sulfur and selenium donors (18331, sulfur-containing alladium(I1) chelates (1834), sulfur-molybdenum compExes (1835), and hydrogen sulfide-hydrogen selenide (1836) systems have also been discussed.
FLUORINE A review of the applications of fluorine-19 NMR (1837) has recently appeared. Theoretical developments in fluorine-19 NMR include calculations of proton-fluorine-19 nuclear spin couplings by the finite perturbation method (1838) and calculation of geminal substituent effects upon fluorine-19 chemical shifts (1839), experimental and theoretical NMR studies of the coupling constants in seven isotropic ethyl fluorides (1840). Fluorine-fluorine coupling has been observed in fluorinated carbohydrates (1841), while hydrogen-fluorine coupling has been given for pentafluorobutane (1842) and 2-bromo-4-fluoroanisole (1843). A solvent and temperature dependence study of H-H, H-19F, and 19F-19F coupling in difluoroethylenes (1844) has also been reported. Proton and 19F chemical shifts were measured for hypofluorous acid (I845), para-substituted fluorobenzenes and 4-substituted 3'- and 4'-fluoro-trans-stibenes(1846) and 1.2-difluoroethane (1847). Fluorine-19 chemical shifts were recorded for hexafluorobenzene (1848), bridgehead substituted fluorobicyclo[2.2.l]heptenes (1849), and in high resolution molecular Zeeman measurements in difluoromethane (1850). Solvent isotope effects on the chemical shifts of complex fluoro ions in water and heavy water solutions (1851) and the temperature variation of the isotope shift of fluorine nuclei (1852) have also been observed. Fluorine-19 NMR has been used in studies of molecular reorientation in solid hexafluorobenzene (18531, aprotic solvent effects on p-substituted fluorobenzenes (1854), protonation of amides by trifluoroacetic acid (1855), poly(vinylfluoride) (1856), mechanism of the reaction of oxygen difluoride and carbonyl fluoride (183'73, 1,2-dihaloperfluoropropanes (1858), and the difluorochlorine(II1) cation ( ~ 5 9 )Other . investigations include rotational diffusion in liquid trichlorofluoromethane (1860), study of micelle structure by fluorine magnetic resonance (18611, variable temperature spectra of 1-fluorocyclooctene (1862) and hydrolysis and NMR studies of fluorine exchange (1863). Fluorine-19 NMR spectra and carbon-13 satellite spectra of some fluorochloroacetones (1864) and aromatic solventinduced shift effects on proton and 19F nuclei of dipolar solutes in benzene and fluoro-substituted benzene derivatives (1865)have also been described. Fluorine-19 magnetic resonance investigations have been carried out on xenon oxytetrafluoride (1866), fluorinated phenyl-tert-butyl nitroxide radicals (1867), Group I1 difluorides (1868), boron trifluoride complexes with some aliphatic and aromatic ethers (1869), boron trifluoride complexes with acetylacetone derivatives (1870), other boron trifluoride adducts (I871), fluoroborate species (1872), and boron trihalide complexes with pyrazine derivatives (1873).Spectra have been utilized in reactions of methylchlorodisilanes (1874),dehydrofluorination and cleavage of silicon nitrogen bonds in boron trifluoridesilylamine systems (1875), intramolecular fluorine exchange in diphenyltrifluorophosphorane (1876), diamagnetic shielding of fluorine-19 nuclei in tetrahedral and octahedral fluorides of nontransition elements (1877), and temperature dependencies of fluorine-19 NMR spectral parameters in tetrafluoroborate solutions (1878). Systems such as phenyl-substituted phosphonitrilic fluoride trimers (1879) fluorosilyl amines (1880), substituent effects on silicon of fluorophenylsilanes, (1881), (pentafluoropheny1)sulfur fluorides (1882), substituted fluorothiophenes (1883),imidosulfuryl fluorides (1884), and fluorine exchange in diorganoselenium difluorides (1885) have been studied by 19F NMR. Spectra for the trifluoroxenon(1V) k-fluorobispentafluorantimonate(V) cation (1886) and complexes of antimony and bismuth trifluorides with
strong fluoride acceptors (1887) have also been described. The sign of the bismuth-fluorine spin-spin couplin and the bismuth quadrupole coupling of the potassium 8exafluorobismuthate(V) powder (1888)has been reported. Fluorine-19 NMR spectra of metal systems include homo- and heteropolyfluoro anions of niobium and tantalum (1889), a spectroscopic study of complex formation between antimony pentafluoride and pentafluorides of niobium (1890), trifluorophosphine complexes of rhodium(1) (1891), interaction of the hexafluoroanions of Group IV elements with cations in solutions (1892), stereoelectronic dependence of metallomethyl substituent effects (1893), o-phenyl derivatives of a-cyclopentadienyl carbonyls of molybdenum and tungsten (1894),low valent transition metal complexes with fluorocarbons (1895), spectrum of the hexafluoroantimonate(V) ion (1896), fluoro complexes of platinum and palladium (1897),tetrafluoroethylene complex of platinum(0) (1898), organotin compounds with partially fluorinated substituents (1899),reactions of tantalum pentafluoride with organic donor molecules (1900), and solutions of niobium(V) in hydrogen fluoride (1901). Shifts induced by tris(dipiva1omethanato)lanthanides (1902) and fluorine NMR chemical shifts in d10 and P4metal fluorides (1903)have also been discussed.
CHLORINE, BROMINE, AND IODINE Silicon-chlorine bonds in some alkylchlorosilanes have been studied by chlorine-35 NMR (1904). Chlorine-35 nuclear spin-lattice relaxation measurements were taken in liquid chlorine (1905), and of chloroauric acid tetrahydrate from 180 to 300 "K (1906). Proton NMR investigations have been made of the liquid hydrogen chloride solvent system (1907), 1-chlorobutane (1908), of hydrogen bonding in chloroform and ether mixtures (1909), chloro derivatives of aliphatic nitriles (1910), chlorosubstituent effects on the rate of nitrogen inversion in l-phthalimidoaziridines (1911), haloacetylenes (1912), and in the reaction between chloral and alcohols (1913). Other NMR studies of halogen compounds include the interaction of halide ions with organic cations containing nitrogen, phosphorus, or sulfur in aqueous solutions studied by NQR relaxation (1914),halogen substituent effects on the circular dichroism of pyrimidine nucleosides (1915), solvation of alkali halides by methanol and mixed solvents (1916), methyl-halogen 1,3-syn-axial interaction (1917), studies of 35Cl, 37Cl, 79Br in aqueous solutions (1918),proton shielding in bihalide ions (1919), and solvation of halide ions in water and dipolar aprotic solvents studied by halogen nucleus NMR (1920). Halogen exchange reactions and barriers to torsion around nitrogensulfur bonds in halosulfinamides (1921),chlorine monofluoride addition to haloimines (1922), tetraalkylammonium bromides and inorganic halides (I923), and complexes of bromine with macrocyclic polyethers (1924) have also been reported. Studies have described the exchange of iodide ion with triiodide ion (1925),solvent effects on carbon-13 chemical shifts in alkyl iodides (1926), weak interactions between naphthalene and alkyl iodides in carbon tetrachloride (1927), stereospecific oxidation of alkenes with iodine tris(trifluoroacetate) (1928), and spectra of the N-methyldiazinium iodides (1929). IRON PMR spectrometric investigations of (1,2-diphenylcyclobutadiene)iron tricarbonyl (1930), olefin-iron carbonyl complexes (1931), synthetic low-spin ferric porphyrins (1932), crystalline bis(cyc1ooctatetraene)iron (1933), fluxional organometallic molecules (1934),bis(pyridinat0)iron(ID)-protoprophyrin- IX complexes (1935), bis(N,N-disubstituted dithiocarbamato)maleonitriledithioleneiron complexes (1936), dithiocarbamato complexes of iron (1937), and antiferromagnetic oxo-bridged ferric dimers (1938) have been reported. Organometallic compounds (1939, 1940), alkyl ferrocenes (1941), bridged ferrocenes (1942), and application of tris(dipivaloy1methanato)europium in the NMR spectrometry of metallocenes (1943) have been discussed. Other studies have included contact shifts of binuclear oxo-bridged iron(II1)porphyrins (1944,
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properties of FeEDTA- in water (1945), addition of methylamine to hexakis(methy1 isocyanide)iron(II) (1946), rearrangement of trin(n-methyl-N-benzyldithiocarbamato)iron(IV) tetrafluoroborate (1947), phenyl-substituted ferric N-ethyl-N-phenyldithiocarbamates(1948),and reartris(N-methyl-N-phenyldithiocarbamarangement of to)iron(III) (1949). Discussions of iron(I1) phthalocyanines as NMR shift reagents for amines (1950), equilibria between iron dinitrosyl paramagnetic species in solutions (1951), Knight shifts in dimeric oxygen-bridged Schiff base-iron(II1) complexes (1952), porphyrin inversion and halogen exchange in high-spin iron complexes (1953), propagation mechanisms of methyl methacrylate polymerization with alkyl-iron and cobalt complexes (1954) and solution conformation of the ferrichromes (1955) have emerged. Structural studies of substituted pyridine complexes-of iron(II), cobalt(II), and nickel(I1) (1956),trans-P(OCH2)3PFe(Cos) P ( O C H Z ) ~ P(1957), . and bacterial iron-sulfur proteins (1958)have incorporated NMR spectrometry.
COBALT NMR studies of cobalt(II1) complexes have described stereochemically nonrigid complexes (1959), octahedral systems (1960), pentadentate cobalt(II1) aminocarboxylates (I961),carboxylato ligands in dicarboxylatobis(ethylenediamine)cobalt(III) complexes (1962), cobalt(II1) malonato-cations (1963), P-diketone complexes (1964, 1965), alkyltetrakis(trifluorophosphine)cobalt complexes (1966), monodipeptide complexes (1967), carbonato ammine cobalt(II1) complexes (1968), methylatobis(dimethylglyoximato)cobalt(III) adducts (1969), tetragonal cobalt(II1) complexes containing tetradentate macrocyclic amine ligands with different degrees of unsaturation (1970) and pyridinato(methyl)bis(dimethylgloximato)cobalt and related complexes (1971). Synthetic and structural investigations have included geometric isomers of bis(L-asparato)cobaltate(III) ion (1972), mixed cyanocobalt(II1) complexes (1973), transdiacidobis(diamine)cobalt(III) complexes of N,W-dimethylethylenediamine ( ( 1974), complexes containing N , N ethylenebis( acetylacetonimine) and amino acids (1975), and solutions of symmetric cobalt(II1) complexes (1976). Cobalt-59 NMR studies have been utilized in isomerization reactions of mer- and fac-Co(en)(NH3)30H2+ ions (1977), potassium hexacyanocobaltate(II1) (1978), aquopentaaminecobalt(II1)perchlorate and cis- and transaquoamminebis(ethy1enediamine)-cobalt(II1) bromide (1979), and cobalt nitrosyl halide phosphine complexes (1980). Chemical shift data have been reported for some cyanocobalt (ID) complexes (1981), cobalt(II1)-pentaamine complexes (1982), and other cobalt(II1) compounds (1983). A deuteron magnetic resonance study of perdeuterated aquopentaamminecobalt(II1) perchlorate (1984) has been completed, while l9F NMR spectra have been used in studies of the transeffect in some cobalt(II1) complexes (1985) and (fluoroalkyl)cobalt(III) Schiff-base (1986) complexes. Trivalent phosphorus derivatives of cobalt carbonyls (1987), cobalt(II1) and rhodium(II1) N,N’-dialkyldithiocarbamates (1988), and terpyridine complexes of cobalt(IT[) and iron(I1) (1989) have been studied by NMR spectrometry. Studies of the protonation of the peptide linkages of bis(glycylg1ycinato)-cobaltate(II1) (1990),and complexes of cobalt(II1) with glycyl-L-histidine (1991) have been completed. PLATINUM AND PALLADIUM The anisotropy of platinum-195 NMR shifts in crystalline platinum(I1) compounds (1992) and high-resolution spectra of platinum-acetylene complexes (2993)have been discussed. Proton NMR spectra have been presented for some trimethylplatinum(1V) compounds (2994), conformers of an isoquinoline-platinum(1V) complex (1995),cationic acetylenic platinum(I1) compounds (1996), a platinum(I1)-x-vinyl alcohol complex (1997), crystalline tetracyanoplatinate(I1) and potassium tetracyanoplatinate bromide hydrate (1998), platinum(I1) olefin complexes (1999). trans-dichloro(amine)(olefin)platinum(II) com326R
plexes (2000),complexes with six membered chelate rings (2001, 2002) and dimethylplatinum(1V) cations (2003). Carbon-13 NMR has been utilized in a comparison of the bonding in zero- and divalent plantinum-olefin nild -acetylene complexes (2004). Coupling constants have been reported for some platinum(I1)-amine complexes (2005), diamine complexes of platinum(I1) and (IV) (2006), and methylplatinum(I1) complexes containing tertiary phosphines (2007).The origin of line broadening in the hydridic NMR of (isothiocyanato)platinum(II) complexes (2008) and phosphorus-31 NMR of trialkylphosphine complexes of platinum(I1). (2009)has been discussed. NMR spectra have been reported for bis(N,N-dialkylthiose1enocarbamato)-nickel, -palladium, and -platinum (2010), sulfide (thioether) complexes of platinum(I1) and palladium (11) (2011) , and P - allylic palladium Schiff - base complexes (2012). Low temperature NMR studies of dimeric palladium salts (2013), and PMR coupling constants in a-allyl palladium complexes (2014) have also been described,
COPPER, SILVER, AND GOLD NMR spectra have been utilized in investigations of copper(1) cationic olefin complexes (2015, 2016) copper(1)triphenylphosphine (2017) compounds, and copper(1) halides with bis( diphenylphosphino) methane and 1,2-bis(dipheny1phosphine)ethane (2018). Dimeric copper(I1) benzoates (2019), dichloro(pyridazine)copper(II) (2020), dimeric cupric compounds (2021). copper benzoate (2022), binding of copper(I1) by ribonuclease A and ribonuclease S-peptide (2023) and Alcian Blue 86X (2024) have been studied by NMR techniques. Other copper(I1) investigations have included hydration and structure of copper(I1) complexes in solution (2025), indirect nuclear spin coupling between copper(I1) pair in copper acetate monohydrate (2026), coordination rearrangements of copper complexes during reactions with bases (2027), characterization of a new class of diamagnetic copper(II) species (2028), and proton relaxation in copper acetate (2029). Nuclear magnetic resonance studies of silver ions and 1,3,5-trinitrobenzene complexes with heterocyclic compounds (2030)have been described. Among the NMR studies of organogold complexes, dimethyl gold halide complexes of mono- and difunctional thioethers (2031), organogold(II1) compounds containing pyridine and tertiary phosphines, arsines, and stibines (2032), molecular and cationic alkylgold phosphine complexes (2033), some dihalo- and dialkyl(N,N-dialkylthioseleno-carbamato)gold(III) (20341, and benzylsulfidechlorogold(1) (2035) compounds, and [p-tolyl(tripheny1phosphine)gold]triphenylphosphinegold borofluoride (2036) have been reported. Ligand exchange in unsymmetrical dimethylgold(II1) complexes (2037), trends in ( C H ~ ) Z Y A U P ( C ~compounds H~)~ ( Y = C1, CH3, u - C ~ H ~ ) (2038),and studies of ligand substitution processes a t twoand four-coordinate gold atoms (2039) have been discussed. LEAD, ZINC, CADMIUM, AND MERCURY Among the organolead compounds investigated by proton NMR, a study of tetra(2-fury1)- and tetra-(2-thieny1)lead (2040), acceptor properties of some alkynyllead compounds (2042), the magnetic moment of lead-207 (2042), studies of lead(I1)-tetraethylenepentamine heptaacetic acid (2043, 2044), some aryllead tricarboxylates (2045), and the complexing of diethylzinc (2046) have been presented. Lead-207 satellite spectra and lead-207 proton long range coupling constants of the symmetrical isomers of tetrafuryl- and tetrathienyllead (2047) have been exhibited. NMR spectra have been included in spectrometric studies of amino polycarboxylate chelates of divalent lead, zinc, cadmium, and mercury (2048) and 0ethyl thioacetothioacetate and its zinc(II), cadmium(I1). and mercury(II) derivatives (2049). Zinc compounds which have been studied by YMR techniques include zinc-L-aspartic acid (2050), halo(diethylthiourea)zinc(II) complexes (2051), and di-4-pentenyl-
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zinc (2052). Metal alkyl-active methylene chelate compounds with a,@-unsaturatedcarbonyl compounds (2053) and spectra of zinc, cadmium, mercury, aluminum, gallium, and indium vinyl derivatives (2054) have also been presented, while fluorine-19 NMR has been used in identification of zinc, cadmium, and mercury hydroxyfluorides (2055).
Complexing of cadmium iodide with pyridinecarboxylic and aminobenzoic acids (2056), the behavior of dimethylcadmium toward OCN- and S C N - (2057), exchange studies in dimethylcadmium, dimethylzinc-trimethylindium, and dimethylcadmium-trimethylgallium (2058), and cadmium, zinc, and lead complexes of polyglycine peptides (2059) have been discussed. Temperature dependent NMR spectra of some methylcyclopentadienyl metal compounds (2060) have been described. PMR techniques have been incorporated in studies of methylmercury salts of carborane carboxylic acid (2061), mercury-203 exchange studies of allylmercury systems (2062), bis( perfluoroviny1)mercury (2063), fluoroarylmercurials (2064), cyclopentadienylmercury compounds (2065, 2066), organomercury compounds (2067), complex mercury(I1) cations (2068), dialkylchlorosulfenamides with silver and mercury(II) fluorides (2069), and solvation studies of RHgMes compounds (2070). Bis(trimethylsily1)mercury and diorganomercurials (2071) and mercury-199 nuclear shielding constants in organomercury compounds (2072) have also been reported.
PARAMAGNETIC COMPLEXES AND COMPOUNDS In addition to the revipws cited earlier, the use of ESR and NMR methods for the elucidation of electronic structure of transition metal complexes has been discussed (2073). Chemical shifts in paramagnetic gas mixtures (2074), nuclear and electron spin polarizations during radical reactions (2075), numerous studies of the NMR spectra of free radicals (2076-2088) and interactions of free radicals with transition metals (2089), nitrogen-14 magnetic relaxation of dimethylformamide solutions containing manganese(II), nickel(II), and cobalt(I1) ions (2090), proton relaxation in N-methyl-y-butyrolactam and hexamethylphosphoramide solutions containing Mn(I1) ions (2091), water-exchange studies on Mn(I1) NTA and EDTA complexes (2092), lecithin dispersions in water (2093) and peptide complexes (2094) with Mn(I1) ions, studies of Mn(II1) porphyrin complexes (2095. 2096), P-H spin decoupling in solutions of paramagnetic ions in phosphorus compounds (2097, 2098), H-H spin decoupling in solutions of paramagnetic species in amines (2099), proton
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and deuteron NMR shifts in paramagnetic complexes (2100-2102) anomalous shifts in apparently diamagnetic osmium acylaryldiazine complexes (2103), binuclear oxobridged iron(II1) 2,2'-bipyridine complexes (2104), and the use of the tetraphenylborate anion as an alternative to complexation with lanthanide shift reagents (2105) have been reported. Several superb studies of chromium(I1) chelates (2206-2110) have demonstrated the use of NMR studies in determination of orbital ground states, electronic effects on methyl rotational barriers, and a T spectrochemical series for diimine ligands. NMR studies of line broadening by tris(ethylenediamine)chromium(III) (2111) and a-cyclopentadienylchromium(1) cations (2122) have been reported. Theoretical (2113) and experimental studies of numerous paramagnetic amine adducts (2114-2125) of nickel(I1) acetylacetonate, theory of contact and dipolar NMR shifts of Ni(I1) complexes (2126), studies of pyridine and picoline Ni(II) complexes (2127, 2128), diamagnetic and paramagnetic Ni(I1) Schiff base and porphyrin compounds (2129-2143), adducts of Ni(I1) dithiophosphates (21442149), Ni(I1) nitrilocarboxylates (2150), calculations for the tris(o-phenanthroline)nickel(II) cation (2151), Ni(I1) complexes with phosphine ligands (2152, 2153), nickelocene and nickelocenium cations (2154, 2155), Ni(I1) in aqueous solutions (2156-2159), Ni(I1) dionato (2160, 2161), flavoquinone (2162), triazine ligand (2163), and monohalo tridentate ligand (2164) complexes have been described. .~umerous studies of adducts of Co(I1) P-diketonates (2,16, 2165-2172) have been reported, as have studies of a-cyclopentadienylcobalt complexes (21 73, 21 74), borabenzene colbalt complexes (2175), Co(I1) human carbonic anhydrase C (2176) and interactions of Co(I1) with adenosine triphosphate (2177), acetonitrile (2178), thiourea and related ligands (2179), nonaqueous solvents (2180), aqueous solutions (2181-2183), tetrafluoroborate anions (2184), and triethylenetetramine (2185), bis(salicyla1dehydato)pyridazinecobalt(I1) (2186), Co(I1) porphyrin complexes (2187), Co(I1) phosphine complexes (2188, 2289) Co(I1) 4methylpyridine complexes (2190), hydro-tris(l,2,4-triazol1-yl)boratocobalt(II) (2191), and ion pairs forme? by Co(I1) bis(tripyrazoly1methane) ions and hexafluorophosphate ions (2192) in solution. In addition to the widespread utilization of lanthanide shift reagents, numerous reports are available concerning paramagnetic uranium(1V) organometallic complexes (2193-2198) as well as several accounts of the NMR spectra of diamagnetic and paramagnetic lanthanide and actinide complexes (2199-221 7 ) . Magnetic multipoles and the "pseudo-contact" chemical shifts of relevance to work with lanthanides have been treated theoretically (2218).
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