(64) Pease, R. F. W., Hayes, T. L., Nature 210, 1049 (1966). (65) Pease, R. F. W., Hayes, T. L., Science 154, 1185 (1966). (66) Pedler, C., Tilly, R., J . Roy Microscop. SOC.,86, 189 (1967). (67) Rambourg, A,, Leblond, C. P., J . Cell Biol., 32, 27 (1967). (68) Reimer, L., “Elektronenmikroskopische Untersuchungs und Praparationsmethoden, 2nd ed., Intercont. Med. Book Corp., New York, 1967. (69) Remsen, C., Lundgren, D. G., J . Bacteriol. 92, 1765 (1966). (70) Revel, J. P., Karnovsky, M. J., J . Cell Biol. 33, C7 (1967). (71) Rodger, A. W., “Techniques of Autoradiography,” Elsevier, Amsterdam, 1967. (72) Salpeter, A I . M., Methods in Physiol. 2, 229 (1966). (73) Salpeter, M. &I Bachmann, ., L., Salpeter, E. E., J . Cell Biol. 35, 119A (1967). (74) Scheuer, P. J., Thorpe, RI. E. C.,
Marriott, P., J . Histochem. Cytochem. 15, 300 (1967). (75) Seligman, A. M., Plapinger, R. E., Wasserkrug, H. L., Chandicharan, D., Hanker, J. S., J . Cell Biol. 34, 787 (1967). (76) Seligman, A. M., Ueno, H., Morizono, Y., Wasserkrug, H. L., Katzoff, L., Hanker, J. S., J . Histochem. Cytochem. 15, 1 (1967). (77) Seligman, A. M., Wasserkrug, H. L., Hanker, J. S., J . Cell Biol. 30, 424 (1966). (78) Sevier, A. C., Anat. Rec. 157, 403 (196i). (79) Sjostrand, F. S., “Electron Microscopy of Cells and Tissue: Instrumentation and Techniques,” Vol, I, Academic Press, Xew York, 1967. (80) Steere, R. L., J . Biophys. Biochem. Cytol. 3, 45 (1957). (81) Sternberger, L. A., Hanker, J. S., Donati, E. J., Petrali, J. P., Seligman, A. M,, J . Histochem. Cytochem. 14, 711 (1966).
(82) Sternberger, L. A., Zbid., 15, 139 (1967). (83) Stevens, A. B., Methods in Physiol. 2. 255 (1966). (84) Swift, J. A.,Saxton, C. A., J . Ultra. Res. 17, 23 (1967). (85) Warshawsky, H., Moore, G., J . Histochem. Cylochem. 15, 542 (1967). (86) Weibel, E. R., Kistler, G. S., Scherle, W. F., J . Cell Biol. 30, 23 (1966). G., . Wetzel, B. K., (87) Wetzel, &I Spicer, S. S.,Ibid., 30, 299 (1966). (88) Williams, M. A., Meek, G. A,, J . Roy. Microscop. Soc. 8 5 , 337 (1966). (89) Wischnitzer, S., Int. Rev. Cytol. 22, 1 /rncv.r
\ I Y U I ).
(90) Wolff, H. H., Zed. Zellforsch. 73, 192 (1966). (91) .Zobel, C. R., Roe, J. Y. IC, Biochzm. Biophys. Acta 133, 157 (1967). The work of Dr. Greider was supported in part by National Institutes of Health Grant No. AM 10480. She is the recipient of Research Career Development Award CA-31,237 from the National Cancer Institute.
Nuclear Magnetic Resonance Spectrometry Jerry P. Heeschen, Chemical Physics Research laboratory, Dow Chemical Co., Midland, Mich.
N
UCLEAR
MAGNETIC
RESONAKCE
(NMR) continues to provide new and exciting insights into the nature of matter. Typical of all areas of scientific research, the number of publications is forbidding. This is particularly true for high resolution proton NMR, which has become a standard analytical tool in organic, bio-, and organometallic chemistry. Even after “eliminating” papers that simply list N l l R data as part of the routine structure characterization, one abstracting service is averaging about 3000 references per year (1669). This review covers material published from July 1965 through June 1967, with few exceptions. An attempt is made to summarize or refer to developnients pertinent to the broad understanding and practice of N M R spectroscopy. Special attention is paid to theory, instrumentation, and techniques. Attention is given, as well, to special information, new areas of application, and significant growth in established areas. The choice of material necessarily is subjective. Little reference is made to metals or materials that display unusual electrical or magnetic properties at low temperature. Many fine reports of structural analysis by high resolution NMR are omitted for sheer lack of space. Introductions to basic theory of magnetic resonance are offered in some good books (333, 1911, 916, 874). High resolution N M R theory and techniques are covered in one book (1499). A two-volume reference treats high resolution N M R thoroughly, presenting both theoretical aspects and a wealth of experimental results for all nuclei (594).
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The analysis of high resolution spectra is treated in one book (429) and coupling in another (1380). Two significant “advances” series were initiated during this period, with some outstanding contributions. The first volume of one contains chapters on theory of relaxation processes, rate processes, paramagnetic molecules, spin spin coupling theory, tabulation of geminal and vicinal H-H couplings, ESR spectra of radicals and ions (2118). A second volume covers sensitivity enhancement, chemical shift theory and other second-order properties, and relaxation of Hz (2119). Another set includes modulation techniques, multiple resonance, computer techniques, and phosphorous compounds (595) plus chemical shift calculations, partially oriented molecules, paramagnetic systems, and density matrix methods for line shape calculation (596).
An extensive review preceded this one, covering July 1963-June 1965 (1303). Another major review was written in two parts (1006, 1007). High resolution developments to 1965 are reported well (246). A review of physical methods includes NMR in 1965 (2159). A wide variety of papers is included in the proceedings of a meeting (1622); N U R papers are included in another published colloquium (1363). Summaries of papers presented a t meetings in 1965 are given (100,612). Some general short introductions to XhlR spectroscopy are noted (959, 1631, 1884, 1924, 1521). NMR and in-
frared spectroscopy are compared for their applications to various types of problems (718,1063). A “Multilingual Dictionary of Important Terms in Molecular Spectroscopy” has been prepared under the sponsorship of ICPAC (1504). Values for fundamental constants are reviewed critically, and tabulated (COS). References are made elsewhere in this review to other books, reviews, and chapters on particular topics. INSTRUMENTATION
Spectrometers continue to improve. A useful survey of commercial spectrometers compares many significant features (1975). A list of manufacturers of spectrometers and accessories available in the United States is given (1858). A general discussion of N M R and EPR instruments and use is given (259). A glimpse of the future was offered in talks on computers by C. H. Sederholm, R. H. Sparks, and R. H. Ernst a t the 8th Experimental KMR Conference (616, 288). General uses proposed include data acquisition, both on-line and offline, and on-line control of irradiating frequency(s) including double resonance; and even complete automatic analysis of spectra by use of appropriate large iterative routines (Sederholm). The decision among use of a hard-wired logic versus small dedicated computer versus time-sharing on a larger machine will depend upon the particular purpose of the operation. Sparks described a set-up where output of two high resolution spectrometers is read into a moder-
ate size computer on a time sharing basis with other analytical instruments. Ernst described an operating system wherein a small computer is used to control field homogeneity on command, otherwise being used for data acquisition and processing. One may anticipate continued incorporation of computer circuitry into future spectrometers. Computer techniques are treated extensively elsewhere (696). “High Frequency” NMR Using Superconducting Solenoids. Major problems are design and construction of the solenoid and of probe t o give good field homogeneity a t the sample. High resolution work requires a spinning sample as well. T h e state of the art is good. A commercial high resolution spectrometer (protons a t 220 MHz) has been introduced with S/N of 4 0 : l for the quartet of ethyl benzene a t 1% concentration and line width of 1.2 Hz for acetaldehyde (2087). A variable temperature probe is used. Other high resolution spectrometers are described, one for protons at 200 MHz (1678), another a t 180 MHz with 5 x resolution (1829,1828). A spinning sample single coil probe, giving -1 Hz resolution at 132 MHz, is built with cylindrical symmetry in all critical parts in order to minimize field distortion due t o magnetic susceptibility of materials (1438). A spectrometer is described for operation between 600 and 700 MHz t o observe samples a t very low temperature; the basic design is applicable for use from 200 to 1000 AIHz (1029). ;1 super-conducting solenoid was used t o study Rh, Pd, and Ag metal a t 1O-4’ K (1529). Another spectrometer at 70,000 gauss field is described (1251). High Resolution Spectrometers. Spectrometers utilizing superconducting solenoids are discussed above. A detailed introduction to N M R spectrometers includes description of the various units of some commercial high resolution instruments (914). A significant advance is offered by the application of Fourier transform spectroscopy, where the signals resulting from a sequence of short R F pulses are stored, then Fourier-transformed to conventional spectrum presentation (611). The authors point out that a spectrum with sensitivity equivalent to the normal method is obtained in about 0.01 of the time, yielding sensitivity improvement by a factor of 10 for the same measuring time. d time-sharing spectrometer with repetition rates to 200 KHz or higher yields base-line stabilized spectra with sidebands so far beyond the carrier that there is no side-band interference even in spectra of nuclei with large chemical shift range (112). A probe for timesharing technique was built for operation a t 56.4, 94.1, and 100 N H z (1693).
Two small “lowcost” (ea $20,000) commercial spectrometers have been introduced. One utilizes an electromagnet (IO%), the other a permanent magnet (2087). Built for routine observation of proton spectra a t 60 MHz, they offer spin-decoupling but no variable temperature operation. Specifications compare favorably with medium-priced instruments. Spectrometers utilizing internal K M R stabilization (lock on a signal within the sample being observed) have been described (1629, 1321, 655). One (1629) uses a foreign nucleus of type other than that being observed, for a sideband oscillator; the others are homo-nuclear locked. A new-type oscillator used to observe H20 a t 30 MHz gave accurate and fast indication of field fluctuations, up to 100 Hz, and should be adaptable to magnetic field control (1088). Simple modification of a commercial internal-homonuclear-locked spectrometer permits use of higher modulation frequencies for observing spectra covering a large range of chemical shifts (523, 1336). A method is described for converting a Varian D-1-60EL spectrometer to frequency and/or field lock (789). Other spectrometers reported include a permanent magnet R F bridge system for observing protons while irradiating other nuclei (784), another with spin-decoupling capabilities (1120), one with a frequency multiplier and autodyne switching (1737), and a permanent magnet-crossed coil system for observing 31Pwith 5 x 10-8 resolution (1816). Brief mention is made of a commercial analog frequency sweep spectrometer (821, 1869), and of a commercial digital frequency sweep spectrometer (2124, 1859), both to observe
W. Conversion of a T’arian 40 1 I H z spectrometer to 70 J I H z required conical pole caps and Golay shim coils (1139). Conversion of a 20-40 MHz spectrometer t o 60 AIHz is described (1320). A method is given for modifying a commercial integrator/decoupler unit t o achieve frequency-swept decoupling (2094). A hetero-nuclear double resonance device is outlined (643). Xicrowave planar triodes were investigated as low-noise preamplifiers in the band 10-100 MHz. A preamplifier operating with optimum source conductance gave a minimum noise figure of 0.35 db a t 24.3 1 I H z (1253). A means for suppressing one of the two sidebands of a frequency modulated R F signal is described for a double resonance apparatus (2063). A brief description is given of experimental apparatus for producing an incoherent R F field to achieve heteronuclear decoupling with random noise (609). Increased accuracy in obtaining line positions has been achieved by use of a
time base generator and digital readout (1680) . Wide-Line Spectrometers. A lowpower transistorized spectrometer, with sensitivity comparable t o t h a t of the best vacuum tube equipment, utilizes frequency modulation a t frequencies high enough to minimize l/f transistor noise (201). A spectrometer for the range 2-40 MHz with crossedcoil induction probe and 2-90 MHz with a parallel T bridge uses simple R F circuits. Simple modification of a commercial 8-16 MHz probe to 40 MHz is described, and sensitivity compares favorably with that of commercial spectrometers (2039). Another spectrometer is assembled from standard components (1852). The time-sharing high resolution spectrometer utilizing repetition rates to 200 KHz or more gives undistorted broadline absorption spectra as well (112). Related to this are reports of the use of high-frequency-high-amplitude modulation to observe broad-line spectra (1600, 1223). A discussion of existing methods for observing strongly magnetic materials is given, followed by description of a variable frequency transmission line spectrometer with servo-correction of background; only ca 10 mg of sample is required (1852). .4 Q-meter variable frequency spectrograph gives quantitative zero-field signals with sensitivity of 5 x in absorption and in dispersion (2088). A pulse technique, with boxcar integrator, is used in a spectrometer which plots directly the absorption lines of a sample receiving ultrasonic energy from a transducer; it is possible to observe saturation in samples with long T1(1025). Variable frequency X M R oscillators of the Robinson type are reported (571, 627). A single coil spectrometer was converted to dual purpose NAIR and KQR (140). .A transistorized probe from 8 to 130 MHz, used as a field measuring device with H 2 0 , avoids the need to remove most of the circuit well away from the stray field of the magnet (1776). Signal-to-noise ratio may be improved by incorporation of an electronic integrator (2100, 2046). In one case, the arrangement can be adapted to be used as magnetic field stabilizer or to measure temperature-dependent magnetizations (2046). Experimental data are in accord with a theoretical study of the line shape obtained when both resonance circuits of a two-circuit autodyne are set on different frequencies, wl, and w 2 , which differ from 130
(42).
A pressure-dependence study of the Knight shift in Cd used a spectrometer field-frequency locked to 23Na in N a metal (1187). An apparatus is described which allows XMR measureVOL 40, NO. 5, APRIL 1968
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ments a t pressures higher than had been possible previously (392). Pulse Spectrometers. Two commercial spectrometers are available. One (1562) is a crossed-coil system, 2-100 MHz, with recovery time as low as 1-3 micro see. The other is a single coil system 5 6 0 MHz, with 6 psec. recovery time (1365). An instrument suitable for measurements in the rotating frame simultaneously applied H1 and a static field pulse, h,, for time t = 77/7d2in T1 order to align the nuclear magnetization along H I . h, is then turned off, returning H , to the resonance value, and H 1 is turned off at varying times following this. The resulting free induction decays then yield T P values. For solids h, = 1H11 -4 gauss, and correlation times -70 psec to 30 msec can be observed at temperatures from -195’ C to +150° C (1056). Block diagrams are given for other rotating frame experiments (1288, 1027). A spin-echo spectrometer for weak field measurements, a t frequencies between 40 MHz and 1 MHz is described (1954). The description of a spin-echo spectrometer operating at 2-34 ,MHz and -180’ C also reviews the principles of the spin-echo method (364). A high power pulsed spectrometer is discussed (958). An apparatus for observation of spin-echo and free induction decay in R b vapor detects the RF modulation of polarized light transmitted through the pulsed cell (1150). A spin-echo spectrometer was designed primarily for chemical exchange studies (14).
New experimental conditions and a special spectrometer are described for observing weak signals from gases, measuring their T 1 / T Bvalues directly (430, 431). Very weak ?;SIR signals and particularly narrow lines at unknown frequency may be detected without paramagnetic additions, by a pulse technique (1089). Construction parameters are discussed for coils to produce pulsed field gradients for spin echo diffusion studies; a circuit diagram for the current supply is included (2012). A variant of the pulsed-gradient, spin-echo method employs three radio frequency pulses to study multicomponent systems (240). An analysis of several possible input circuits for free precession signals indicates that an untuned transformercoupled input circuit is superior (1646). Improved designs of single-coil probe circuits for pulse experiments are described (1340, 823, 1949, 1032). .$ high stability “boxcar” integrator for fast transients overcomes drift problems common to previous designs (1110). A relatively simple method is proposed for “regenerating” the initial amplitude of a free precession decay, which ordinarily is distorted by amplifier reaction (1441). An attachment to the
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Varian DP-60 spectrometer allows Tzto be measured by the Carr-Purcell technique. Included are details for obtaining correct setting of 180’ pulses and eliminating effects of linear field drift (1434)*
E N D O R (Electron Nuclear Double Resonance). A spectrometer operating at 35,000 MHz ( N M R frequencies 1-500 MHz) is described and applications discussed (425). Apparatus and techniques for E S D O R of free radicals in solution are described (995). Nuclear polarization and relaxation are observed a t ca 175 gauss in another spectrometer (8.46) and moderate resolution for protons is attained at 3300 gauss in another (1103). A method for simultaneous scanning of the field and maintaining proper NMR frequencies permits continuous recording of the polarization curve (1145). Special Spectrometers. A review on optical pumping covers procedures for nuclear orientation and its optical detection (412). A spectrometer with turbine for rotating solid samples is described (1844). A flowing liquid spectrometer with 0.1% stability in flow and 1’ C temperature stability polarizes the nuclei in a 7500 gauss field before observation (1802). Another flowing liquid spectrometer (1648) is arranged to cause almost complete, nonresonant, inversion of the nuclear magnetization; this allows decreased flow rate, and makes possible construction of a laser using relatively simple substances. A calorimeter detected passage ~ through S M R absorption of 5 7 Cmetal and 65L1n in RlnFePOc a t 4.2’ K via elevation of the lattice temperature (781).
Sensitivity Enhancement. One can describe approaches t o enhancement in three ways-improved design and construction of t h e spectrometer (including stronger magnetic fields) ; improvement of probe and sample cell design to achieve better coupling of the nuclei to the receiving coil and/or more nuclei in the observed region of the cell; and improved processing of the output signals from the spectrometer. Progress in the first and second approaches is discussed elsewhere in this section on instrumentation; processing of output is discussed here. Ernst’s chapter on sensitivity enhancement (607) is a fine analysis of the various means of attaining sensitivity enhancement. Computer handling of data, such as curve smoothing, resolution enhancement, and time-averaging are treated. Thorough analysis of the time-averaging method (606) and of the use of intermediate passage conditions (610) are published elsewhere as well. As mentioned above, Fourier transform spectroscopy (611)yields “enhancement” by a factor of about 10 over nor-
mal methods for the same running time, although it should be noted that transformation of the data back to a normal spectrum presentation requires the use of a large computer. 0.3 Micromole of hydrogen in a microcell will give a satisfactory spectrum upon time-averaging for one day (1298); this article describes the appropriate interfacing to a time-averaging computer and collection of the sample from an open-tube gas chromatograph. Other trigger circuits synchronize timeaveraging computers with the linear field sweep units of commercial spectrometers (751, 276). Simple circuits afford sensitivity enhancement by causing very slow, stepped, sweep of commercial spectrometers and observing the absorption curve (471) or integrals (SNAIL) (288, 982, 1726).
The zero crossing point of the derivative of a broad-line signal can be detected with an accuracy of about 1,4000 of the line width by use of a time averaging computer programmed to observe the curve only in selected regions-Le., upper off-resonance, near center, and lower off-resonance (932). Sample Cells and External Referencing f o r High Resolution NMR. Sample cells are available from spectrometer manufacturers and a greater variety from other commercial sources (1562, 2169). Sensitivity improvement by use of microcells, time-averaging, and numerical curve smoothing are compared (735). Gas chromatograph effluent may be trapped directly in a spherical-bubble microcell (258). A technique is given for making spherical disposable microcells from melting point tubes (736). Very fine bore capillaries may serve as microcells whose resolution is better than that of spherical bubble cells; liquid height must be ca 1 em for good resolution (1919). Insertion of a glass or Teflon cube in a sample cell well below the liquid level prevents a vortex at high spinning rate (930). An evacuable plastic cell may be constructed of polychlorotrifluoroethylene, with vacuum seals of polytetrafluoroethylene (528). An inexpensive coaxial capillary insert is made by forming a spherical closed end which just fits inside the 5-mm tube (939). It has been found that the substitution method of external referencing may give reduced accuracy, relative to coaxial external referencing, because introduction of a cell into the magnet pole gap can cause a significant change in the magnetic field strength (734,134). Accurate equations describing a nonperfect spherical reference system, supported by experiment, require correction due to magnetic susceptibility of the sphere (734). A method is given for determining deviation from the ideal shape factor for spherical samples (900).
Variable Temperature. X low temperature Dewar, operating on t h e principle of a still, permits sample spinning a t temperatures down t o -196" C (1666). .;i unique arrangement is a spinning Dewar, containing liquid nitrogen, into which is placed a sealed sample capillary (1786). A crossed-coil probe and cryostat are described for attaining and measuring temperatures between 4' and 273" K. (915). I n another cryostat used for pulse work at 20-31' K temperatures were measured to +0.02" K (1452). Continuous flow temperature control devices are described for operation at 80"-300" K, with 0.5' I< per 0.5 hr. stability (1683) and at 78"-523' K with 0.1' per hour stability (114). More efficient cooling to -100' C in a commercial spectrometer was achieved simply by placing an insulated vapor trap between the heat exchanger and the instrument (927). d patent (1031) describes a method for nuclear spin cooling to a microdegree absolute and a relatively high degree of nuclear polarization without generating microwaves, by irradiating the electron resonance of paramagnetic crystals near 0" K. Coaxial thermometers for simultaneous measurement of the spectrum and temperature of a sample are reported, wherein an internal capillary contains a mixture of water, methanol, and HCl for -25" to $90" C (with 0.2" C accuracy) (539), or ethylene glycol plus formic acid a t high temperatures and methanol or formic acid in de-acetone at low temperature (421). An unusual potential thermometer at 13'-29" K is the 53Cr resonance frequency in ferromagnetic chromium tribromide (1869), while 13'mCe in neodymium ethyl sulfate provides a temperature scale below 1" K (206).
Miscellaneous. A device is described which allows a n y orientation of a single crystal in t h e pole gap (897). A phase detector with improved phase selectivity gives better signal-tonoise ratio uhere the signal is weak, (1972). Signal-to-noise ratio from weak hard-to-saturate lines can be improved in a limited oscillator by tapping across a smaller-than-normal fraction of the RF voltage on the coils (572). An electronic control device permitsin dependent regulation of the phase tuning and amplitude of a twin-?' bridge (1435). Four wide-range Xuvistor probes permit magnetic field measurements over the range 12-93 MHz (888). A detailed procedure is given for use of fluorine gas to clean badly blocked coolant passages in water-cooled magnets (1392). D a t a are given for the design of Helmholtz-type coils with cross-sections that are not small compared to the mean radius (61). A patent describes a de-
vice for establishing uniform magnetic field in a simple manner (1002). Two NMR flux-meters for calibrating superconducting solenoids are described (1431, 1804). An NMR magnetometer is capable of measuring fields to better than 1 gauss in 25 kilogauss at liquid helium temperature (934). A high precision fluxmeter is described (2225). Simplification of a transistorized NMR fluxmeter allows operation from 4 to 60 MHz (369). Precision servo-NMR field measuring equipment for the C E R N muon storage ring gives error of 1 2 ppm a t 17.2 kilogauss and coordinates a t which the field is measured with precision better than 0.05 (283). A review of various magnetic measurements for study of magnetic materials includes discussion of YMR and techniques for pulsing and modulating fields, as well as production of fields of all practical magnitudes (676). MAGNETICSUSCEPTIBILITY is the subject of a recent book (1493) and review (1494). The concentric sample X M R techniques have been considered. A variation of a previous method is modified (1219). Coaxial cells can be spun to give susceptibility by measurement of sideband peak height at a given spinning frequency (1946). A new type coaxial cell is evaluated (938). Paramagnetic susceptibility of a liquid or powdered sample can be obtained by insertion of a reference capillary in the center, and measuring its shift from its 'hormal" value by sample interchange (16). OBTENTION OF SPECTRAL PARAMETERS
High Resolution Spectrum Analysis. A book published in this period (429) "provides a thorough treatment of mathematical techniques and essential quantum mechanical ideas required in interpretation of the multiplet structure" of high resolution S M R spectra, and contains practical applications as well. Analysis of high resolution spect r a by various direct (observational) and indirect (calculation) techniques is discussed in one paper (947) and systematic classification and analysis of spectra, including comparison of five methods for an A2Bz spectrum, in another (512). Conditions for equivalence of nuclear spins, such that spin-spin coupling among them is not observable, are presented for the cases of oriented molecules, such as those in liquid crystal solvents and in solids with quadrupolar nuclei (1514). Theoretical proof is given for the validity of an average Hamiltonian to describe molecules undergoing fast periodic internal motion (1897). The use of a full set of symmetry groups for spectrum calculation is discussed, with detailed treatment of the X3AA'X3' system, and found to be more cumbersome than the equally ap-
plicable composite particle technique (2182). Sub-spectral analysis involves the breakdown of complex spectra into a set of simpler spectral patterns. The composite particle model and the effective Larmor frequency approach to such analysis are discussed (499), as well as limitations of the method (500). Available methods for determining the absolute or relative signs of spin-spin couplings are reviewed in a thesis (547). I n favorable cases, spectral analysis can be aided by systematic use of solvent or temperature effects to cause adjustment of multiplet overlap, resulting in perturbations of single resonance spectra similar to those of double resonance spectra (713). Judicious adjustment of temperature was used to obtain critical values of V A - V B in an AB2X3 system, yielding sign values of J A Xand JSx even when J A X = 0 (712). I t may be possible to determine absolute signs of geminal H-H couplings (1929, 1950), and geminal H-F couplings (1951) by their change with solvent. I n the case of H-H coupling, it was found that the coupling becomes more negative as solvent dielectric constant and/or hydrogen bonding increases, the effect being stronger for CHz groups attached to heteroatoms. I n both cases the effect is attributed to electrical interactions. The coupling constants in rotamers can be determined by observing the effect of varying solvent; this method is preferable to varying temperature because of possible temperature dependence of the coupling for a given rotamer ( 5 ) . Of course, spectral patterns may be changed significantly also by varying the observing frequency, in order to aid or verify an assignment. I n one instance the fluorine frequency was reduced drastically, to 6.14 MHz, to introduce second-order features in the spectrum of pentafluoro iodobenzene (an internal lock was used) (1466). Proton spectra were observed a t five frequencies, in addition to decoupling, to obtain relative signs of couplings in some methyl- and ethylphosphonium ions (531); protons were observed at 60 and 100 NHz, IlB at 5, 10, 15, and 20 MHz in the analysis of decaborane-14 (216S), and protons were observed at 100 and 20 AIHz to analyze some cyanine dyes (454). A t the extreme, heteronuclear coupling may be observed profitably in fields of 1.5 gauss and less (551, 167). In the analysis of satellite spectra one must consider small long-range splittings which cause small effective changes in shifts (526,1729, 780,935). I n ABC systems, the terminal transitions (to '-t3/2 levels) can be located by their coincidence with double-quantum transition lines upon inversion of the double-quantum spectrum about its center of gravity followed by a two-fold scale expansion (1203). The average chemical shift (centroid) of an NMR VOL 40, NO. 5, APRIL 1968
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spectrum, which can be useful in spectral analysis, may be obtained simply by extrapolation of the second integral (2139)* A nonconventional means of analysis is by examination of linewidths due to relaxation. Linewidths were calculated by Redfield’s theory for ABX and A2X2systems, yielding relative signs of certain coupling constants which are not obtainable by conventional spectrum analysis (1318). The absolute sign of J X F in CHFClz was shown to be positive, via use of experimental results on fluorine relaxation time and chemical shift anisotropy, in a theoretical investigation of relationships among molecular correlation times, relaxation mechanism, and relaxation times (1342). Analysis of various systems of spin-’/z nuclei continues to receive considerable attention. Perturbation theory is applied to a variety of simpler systems where couplings are much greater than shifts-AB, AB2, AB3, A2B2, and A2B3 (2120) and ABC (193). I n a general article dealing with two and three spin-1/2 systems numerous spectra are reproduced and effects of molecular symmetry and virtual coupling are discussed (151). Improved techniques for simplifying the analysis of A2Bz spectra involve line assignments and intensity rules (511, 1267); in one case a computer is used subsequently to check all possible permutations and give final parameters (126’7). It should be noted that the A2Xzapproximation to an A2B2 system requires that all couplings be small compared to the chemical shift (686, 1305). A nomogram was used in the analysis of ABCD patterns (144). General properties of the X parts of A.BX, spectra (501) and of XJA‘X’, spectra (896, 665) are discussed. Other systems analyzed were six chemically equivalent nuclei with CaU X C, symmetry (1542), ABCX with J A c = J B c cz 0 (676), A B X Y (1767), A2BXz and A2BKk (944), ABB’XX’ (1189), nonrigid AB2X2 (1058), AA‘BB’X and AA’XX’N (1060), A2B2X and A2B2X2 (4’70), AA’XX””X’’’ (boo), AA’BB’B”B”’ (1978), ABB’CXX’ (1928), AA’JfJf’XX’ (123),AA’XX’JfR, and A A ’XX’,11 I’ (1302), ilA ’BB ’X3 (1250), A A ’A ” A ”’XX ’X “X”’ (1059), A d ’A ”A”PP’XX’ (636), ABJ‘QX (212),A3X2X2‘A3’(966), and 1,3,5-~ycloheptatriene (852). Some deceptively simple spectra reported involved large phosphorousphosphorous coupling (1084, 968, 458, 474, i.480, 891, 655) and coupling constants of approximately equal amplitude and opposite sign (1053, 334). Virtual coupling is discussed and illustrated for A B J I X and related systems (28), is the source of asymmetry in the alpha CH2 doublet of n-alkyl fluorides (965), and is observed in the proton spectra of some organophosphorous compounds contain-
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ing two or more phosphorous atoms (931, 278). USE OF COMPUTERS.Computers are used extensively to calculate and analyze spectra. The first level of sophistication involves programming a straightforward calculation of eigenvalues and eigenvectors which in turn yield transition frequencies and their relative intensities. A t the next level of sophistication are iterative programs, which adjust trial parameters to make their calculated spectral line positions match corresponding observed lines. The iteration may operate by comparing line positions (calculated vs observed) or by comparing energy levels (calculated vs “observed” levels whose values are deduced from observed spectral lines). A t the first level, programs are reported for computation of frequency sweep double resonance spectra (816), with discussion of necessary corrections due to Bloch-Siegert shift when an internal lock is used. Most work centered on iterative methods. The problems are attaining convergence to a solution, evaluating the error in the solution, and determining whether the solution obtained is unique. The two types of iterative methods were found to be complementary in a study of their application to identical problems-iteration on energy levels is faster, but yields less accurate results (though probably accurate within experimental error of the observed spectrum) (2195, 1081). Application of damped least squares to iterative analysis can lead to fast convergence (1642). The general method of solving the inverse secular problem enables one to suggest various mathematically possible solutions to N J I R analyses (2038). A major problem in use of iterative methods is assigning calculated transitions to corresponding observed lines. For complex systems, this can be most difficult, especially when appreciable overlap occurs. Programs are described to do this-one obtains positions of overlapping lines and another obtains consistent sets of line assignments by use of frequency and intensity sum rules (1097). Overlapping lines may be resolved rapidly also by use of an analog computer and oscilloscope display (312). Exact analysis of three-spin systems has been given special attention because of its relative simplicity (2156,2195,592, 2081). Iterative programs have been written for or adapted to smaller computers (257, 256, 1291, 1611, 88). A detailed account is given of the application of one program to a five-spin system (679). Multiple Irradiation is a valuable technique for analysis of high resolution spectra. A thorough treatment of the subject has been written (950). In its simplest use, strong continuous irradiation of one absorption effectively
removes the coupling of that nucleus (i‘decouples’’ it) from the spectra of remaining nuclei in the molecule. Conditions for full decoupling of dipoledipole broadened lines (in solids) and indirect spin coupled structure are discussed (1041). Great breadth-e.g., large coupling constants or decoupling all protons-can cause difficulties in many cases. A cleaner approach for heteronuclear decoupling is the use of an incoherent R F field (609) to generate a more even distribution of R F power over a band of frequencies. Detailed analysis of high resolution spectra requires establishing the interconnections of the energy levels among which the observed transitions occur. Such interconnectivity can be established by irradiating one transition with a relatively weak R F field and observing consequent perturbations in other transitions which have one energy level in common with the first. Techniques which have been established earlier are “tickling,” nuclear Overhauser effects (NOE, including INDOR) and transitory selective irradiation (TSI). Systematic methods for applying and interpreting such techniques have been given (111, 722), and NOE applications reported (1166, 1626). A variation on the INDOR and TSI technique uses R F fields capable of saturating the monitored line and adiabatic fast passage through other lines (641). The observed spectrum consists of transient ringing patterns whose initial direction is the same as for ordinary I N D O R ; the results are the same as TSI or I S D O R but possible tickling effects (line splitting) on the IXDOR spectrum are eliminated. A slow pulse modulation technique is useful for observing satellite spectra due to coupling with other nuclei at low abundance (711). The technique alternately adds and substracts the observed spectrum when a pulse at the low abundance nucleus frequency is on or off; chemical shifts and relative signs of couplings can be obtained. This technique is similar to transmission of modulation from one nuclear resonance frequency to another (57, 1275). 14N shifts have been measured to 1 Hz accuracy by observing narrowing of coupled proton lines upon nitrogen irradiation, even when the coupling is not resolved (881, 882, 1416). S O E has been used to establish close proximity of one magnetic nucleus to another in a molecule, even in the absence of coupling between them ( 6 4 , while in another study intermolecular KOE was found to be widespread in liquids (1274). Double resonance due to irradiation of 37Cl is observed in the free precession decay of 2 3 S ain a single crystal of NaC1, in accord with predictions (2062). Very small, unresolved splittings in an ABCX spectrum were obtained by
double resonance and line shape analysis (687). The sign of a small long-range splitting in an ABCX system was obtained by irradiating the ABC portion strongly and observing the asymmetry in the X portion (685). Double resonance has been used to observe exchange processes-nuclei saturated at one site carry the saturation to another, monitored, signal upon exchange. Kinetic data were obtained in this way for inversion of cyclohexane-dll (65) and for hydrogen-carbanion exchange (265), while the effect is only reported for (18)-annulene (518) and exchange between water and phenolic OH in CDC13solutions (650). Although saturation transfer may reduce the signal of a monitored line it does not remove spin-spin splitting between that line and other nuclei-e. g., HOCH splitting when the O H exchanges slowly with irradiated H20 (744). A fully quantitative description of double resonance spectra must necessarily include contributions from various modes of relaxation, which are the source of Overhauser effects. A general technique is presented for exact solutions for many-level multiple-resonance problems, including application to NLIR experiments where relaxation is occurring (708). Theories are given for relaxation effects in weakly-coupled (1721) and strongly-coupled (1420, 1557) systems. The latter theory was modified to treat NOE in complex systems (498). The double resonance spectrum of a single spin-1/2 nucleus (4.3)is shown to give relaxation time via line shape and intensity changes (807). The relationships between linewidths of irradiated and observed resonances in tickling and decoupling experiments were analyzed; and permitted deduction of the 13C line width upon observing the 13C satellite in the proton spectrum of CHCll as well as estimation of PC-CI -49 Hz (714). Relaxation effects were neglected in a perturbation method to compute line intensities for double resonance of a system of coupled spins (141). The measurement of nuclear Overhauser effects has become important in the evaluation of relaxation mechanisms in liquids. A detailed theoretical discussion was applied to such a study of difluoroethylenes (1181). A variation on the transient method, applicable to high resolution spectra, consists of applying “long” pulses of radiation to a single line and observing other lines when HB is off-this eliminates normal double resonance effects (808). Another theoretical study of transient and steady-state Overhauser effects develops the analogy between description of relaxation and chemical exchange (9.48). This analogy also is noted in another double resonance treatment (609).
ELECTROK X U C L E ~DOUBLI; R RESO(ENDOR) is performed in systems containing magnetic nuclei and unpaired electrons. I t is useful for enhancing nuclear signals by saturating the electron resonance (the Overhauser effect, dynamic nuclear polarization), and for observing nuclear resonance frequencies when the absorptions are unobservably broad due to coupling with the electron, by irradiating the nuclear signal while obqerving the ESR spectrum. A comprehensive description of techniques for solutions of free radicals is given (995). Theoretical studies include description of the ESR spectrum (709, 2137) and treatment of three-spin systems \There the electron and one nucleus are irradiated while a second nucleus is observed (1535, 1537, 1005). Effects of field modulation in solids (1700) and correlation time in liquids (553) were discussed. E S D O R was used to study conformational equilibration in a derivative of the triphenyl methyl radical (996). E K D O R enhancement of I3C a t natural abundance (1556) and 31P(556) was accomplished by addition of 2,4,6-tri-t-butylphenoxy radical to solutions. The effect of relaxation by paramagnetic ions on line shape is calculated for the AB spectrum and predicted line asymmetry was found (95). Oriented Molecules in nematic liquid crystals give high resolution spectra which contain dipole-dipole and shielding anisotropy effects. This permits precise measurement of many internuclear distances and absolute signs of coupling constants. The measurement of small chemical shift and anisotropy by comparison with the liquid solution is difficult, and a highly symmetric internal reference should be used (299). Interaction between permanent electric dipole moments of solute and nematic solvent was found to have negligible effect on the average orientation of some chlorinated benzenes in various solvents; and orientation energies were correlated by regarding only the dispersion forces (1827). A general spin Hamiltonian is given, and applied to benzene, fluorobenzene, and hexafluorobenzene (1958). Analysis of a 3-proton system with Cz symmetry and a CH3-H system is presented in terms of dipole-dipole couplings and chemical shifts (601). The tetrahedral molecules tetramethylsilane and neopentane show evidence for slight closing of methyl groups parallel to the field (O.lo), but the smallness of the effect lends good support t o the simple general assumption for analytical purposes t h a t molecular geometry is independent of orientation in the nematic solvent (1959). Other molecules studied were acetylenic compounds, acetonitrile, and methanol (602); cyclopropane and cyclobutane (1439); CH3F NAKCC
(174); and (CJ clobutadicne) iron tricarbonyl (2197). In addition, KMR spectra of various nematogenic substances them-elves, in the nematic phase, were examined (1793). PARTIAL ORILSTATIOS,BY ELECTRIC FILLD, of polar molecules in the liquid phase has been notably unobmvable since the first repoit in 1963 (300) of a successful experiment n ith para-nitrotoluene. T n o group< of inlestigators have attacked the problem theoretically, to predict the magnitude of effect., and experimentally, with methods that should be much more sensitive than the original high resolution expel iment. Rotating-frame puLe technique was applied to nitrobenzene and para-nitrotoluene n i t h no succes (1862). The other group alqo diwuqsed the theory (486, 487) and attempted to ohseive effects of dipole-dipole interaction in nitlomethane via high-reiolution N M R during application of an alteinating applied electric field (1361, 1360). I n both cases, the authors concluded that the Lorentz cavity model for the liquid overestimates quadratic electric field effects, prewniably because there is strong ordering of electric dipoles. Broad-Line Spectra. Very broad S M R lines, as for solids a n d quadrupole-broadened nuclei in liquids, are observed b y continuous irradiation t o give a presentation of the absorption curve usually as its derivative (broadline), or by pulse techniques. T h e application of broad-line techniques t o studies of solids is covered here. Two general methods for calculating line shapes give good agreement with experimental results for CaF2. One utilizes retarded Green’s functions (1386), another uSes n.eighted sets of polynomials (1976). treatment of the three-spin-1/2 system in the polycrystalline state was applied to LSeiO(Olc)6 (1757). Line shapes due to anisotiopic interactions of the form a,(3 cos2e - 1) are examined for the case where the Gaussian width is much less than the overall width-special attention is given to the presence of a reasonably strong step a t e = 0’ in the absorption curve (685). The effect on line shape of anisotropic interactions is computed and applied to ’Li in Li-Li3S alloy (683) and studied theoretically for the caqe of dislocation dipoles (828). A t low fields (0-40 gauss) normal perturbation theory does not describe the line positions in a two-spin system because the dipoledipole interaction is not “small” (814). It is shown that asymmetric field gradients cause a decrease in magnetic dipole-dipole coupling among nuclei with integer spins, and coupling to nonresonant spins also is reduced greatly in first order-the results were confirmed by 35Cl spin-echo double resonance measurements of BaC1O3.D2O (1249). This theory is extended to zero field VOL. 40, NO. 5, APRIL 1968
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(pure NQR) (376). An experimental and theoretical method permits determination of the tensors of nuclear quadrupole coupling and paramagnetic hyperfine structure in single crystals (897). The magnitude of the shift in the maxima of N M R lines of polycrystalline solids, due to quadrupolar broadening, can be determined from a knowledge of the dipolar broadening (15). Also for polycrystalline solids, the N M R line shape due to second-order quadrupole interaction with asymmetric field gradient can yield the KQR frequency and asymmetry parameter (1534). The modulation field H, is shown to require a correction term Hm2/2in the second moment calculation, as opposed to earlier values Hm2/4and Hm2/3(2099). A theoretical expression for the first, second, third, and fourth moments of lines for spinning solids was obtained (1856); the calculation of odd moments is useful where anisotropically shifted and asymmetrically broadened peaks occur as well as syrnmetiically broadened peaks, and comparison of the second moment of the non-spinning sample with that of the corresponding main peak of the spinning sample permits separation of direction-dependent and directionindependent parts of the Hamiltonian. Practical formulas are given for analyzing overlapping Gaussian, Lorentzian, or mixed line shapes (477). Generally good agreement has been found between N M R and neutron diffraction values for the H---H vectors of water(s) of hydration in single crystals. In one set of studies of several hydrates (584,586, 586),conclusion was reached that 1) use of peak-peak separation gives fairly accurate values for complex hydrates where centers of gravity cannot be obtained nor corrections made for thermal motions, and 2) the H-H distance by N N R is greater than that from K D (585). The latter paper also notes that apparently "commonly used methods of motional correction for the N M R and S D distances cannot be reconciled unless one or both of the two procedures is seriously revised," then proposes an N M R method that generally should yielg proton positions to better than 0.1A. A theoretical treatment of second moment as a function of crystal orientation yields a maximum of fifteen structural parameters (482), and obtains agreement with S D data for oxalic acid dihydrate. Other studies utilized S M R a n d N D as well (481,1129). Structuredue to dipole-dipole interaction has been calculated for the four-proton system BaBr 2H20 (1333) and the nearly linear fivespin systems KH2F3and NaHzF3 (205). A calculation of second moment and TI was made for a hindered rotor containing two identical spins and moving in a potential with unequal minima; the energy difference between the minima lengthens TI and inhibits the motional 566 R
ANALYTICAL CHEMISTRY
decrease of the second moment (1289). Transition temperatures obtained by K M R line narrowing and calorimetry in the study of free molecular rotation phenomena need not necessarily be the same, on the basis of Fraenkel theory interpretation (279). Line shape and second moment were calculated under simplified conditions for Overhauser and "solid state" effects as a function of NRIR-ESR signal separation (1144). Two studies of thallium halide single crystals yielded isotropic exchange interaction and pseudo-dipolar interaction; they combined double resonance data with TI second moment for the chloride (398) or with T1 and halogen line widths (1815). E N D O R successfully enhances to observable intensity the proton spectrum of CH3CHCOOH, a minor radical product from the X-ray irradiation of succinic acid (1730). The dispersion mode of a nuclear spin population is described theoretically, using the Redfield formalism, including relaxation and period of the modulation field; N M R parameters can be obtained in this way when absorption measurements are not possible (1106). Angles of the disorientation of blocks in ruby crystal were estimated on the basis of the theory of the quadrupole effect on the nAl spectrum for different orientations of the trigonal crystal axis; angles a9 > 24' are based on predicted splitting of satellite lines, while smaller angles are estimated (1612). The autocorrelation time of paramagnetic ion impurities in dielectric crystals might be obtained by measuring K M R linewidth and Ti,as supported by preliminary results on CaFz doped with E u (464). A study of ammonium chloride TI, at pressures to 2000 atmospheres and temperatures from 175" K to 290" K, showed marked decrease in the activation energy for the TI process a t high pressure, both above and below the Lambda point (2053). Rotating Solid Samples. Other reference t o rapidly rotating sample technique is made in t h e instrument and broad-line sections. T h e close analogy of rotating frame t o rotating sample is discussed in the section on pulse methods. I t is shown theoretically t h a t t o a first approximation the quadrupole interaction contributes nothing to the second moment of the center line for an angle of 54.7' (1857). Use and theory of the technique (at 54.7') is described for a number of phosphorous compounds; it is shown that the chemical shift tensor may be replaced by its isotropic value (69). Two pulse studies of relaxation in rotating samples are noted. I n one, on ?vlg,PZ, Zn3P2, and AlP powder, it was concluded that indirect spin-spin coupling limits determination of TI and Tzat high spinning rates, and phosphorous shifts and nonequivalent P-P couplings were deter-
mined (1108). 23Na free induction decay was observed for S a C l a t 54.7" and a t 90" (451). Line Shape Analysis and Modulation Effects. Two fast, graphical, methods are given for analysis of symmetrical line shape as a mixture of Lorentzian and Gaussian curves (1699, 136). Frequency modulation of the Larmor frequency causes sidebands; appearance may be explained on the basis of a magnetic dipole in a quantized R F field (1647). A method is proposed for rapid measurement of very short T I and TZ(to see.) values by analysis of the Fresnel representation data obtained from amplitude modulation of the R F signal (98). TI also may be obtained from the dispersion line shape as a function of modulation frequency (1520). The effect of magnetic field modulation on S M R line shape for solids under strong saturation ccnditions was studied theoretically; the results are applicable over the full range of modulation frequencies when the modulation amplitude is small compared to line width (1818). A related experimental study of the Bloch-Siegert effect with frequency modulation observed line intensity changes as a function of modulation frequency and modulation index when the side-bands were not fully resolved (333). Other studies of modulation effects covered Lorentzian lines (89) and two-frequency modulation (1174). Pulse Techniques. Measurement of TiR,T I in the rotating frame, can be achieved when T z > T~ (molecule), are altered to the case 7, >> T I ; it is suggested that the latter situation describes most proton cases reported to date (1191). A general expression has been derived and tested for isotropic proton hyperfine interaction constant caused by qpin density a t a carbon atom in an aliphatic chain (108). The effects on lineividths and shifts of electron transfer between a diamagnetic molecule and its anion are worked out to give exchange rates and signs of spin densities (219, 220). The conditions under which one can observe N J I R spectra of organic free radicals are diqcuqsed (905). The measurement of spin density sign by contact shifts, in 1- and 1,4-alky1 substituted benzene anions permits evaluation of the contributing factors (945, 218). ''0 contact shifts and hyperfine interactions have been obtained for water in the hydration shell of nickelous ions (417 ) and for l I n ( I I 1 ) tris(acety1acetonate) ( l 9 l 4 ) . The hydrogen bonding of chloroform with Co(I1) and Si(I1) complexes results in strong proton shielding which is interpreted as showing marked dominance of contact contribution over pseudo-contact (1749). Ion pairing is implied by shifts of tetrabutyl ammonium protons in the presence of Co(I1) and Ni(I1) complexes (1190, 972). Other studies of contact shifts in complexes with transition metals have been reported for Co(I1) and Si(I1) (2220, l l S 7 ) and Fe(I1) (1668, 1326). A number of aliphatic nitroxide radicals have been studied by both proton N l I R and ESR (1172). Proton Spectra. Proton NMR analyses of a large variety of organic compounds are reported. Some large tabulations of shifts, and sometimes couplings, are noted for formyl proton
of aliphatic aldehydes (1133); aliphatic esters (1785); p-diketone enol ethers (76); secondary straight chain alcohols and their 3,5-dinitrobenzoate derivatives (796); hydrocarbon olefins (1959, 1276) ; unsaturated fatty acids (1681); acrylic and crotonic compounds (1184, 2069) ; cis- and trans-stilbenes (856, 857) ; cycloalk-2-enones (912); vinylic protons of substituted styrenes (865); alkylcycloheptatrienes ( I 109) ; nitrogen-containing organic compounds (1922); tertiary amines (1248); Nmonosubstituted methylamines (716); various organics (2106); and a general correlation chart (1462). Some significant molecules whose KXIR spectra have been analyzed are cyclopropenone (270); butatriene (697); cumulated trienic ketones (176); previously unreported cyclohexanetriols (1524); the monohalobenzenes (1727); S-decoupled pyridine over a range of pH values (1445); isoquinoline (199); hexavinyl benzene (224) and Neisenheimer complexes (345). Proton ?;AIR and IR spectra of pyrroles, thiophene, and furan are compared (350). Larger series of aromatic compounds include donor-substituted polycyclic aromatics (2227); monosubstituted benzo[c]phenanthrenes (1404) ; polycondensed aza-aromatic derivatives (1407); xanthones (305); and 2-methyl-benzoxazole, -benzthiazole, and benzselenazole and derivatives (2036). Some sulfur-containing compounds related to long-chain fatty acids are described (1679); and qpectra analyzed for 1,2-dithiol-3-ones and 3-thiones (287) and thiophenes (2003,2000, 1105). A variety of organophosphorous compounds have been reported (1489, 1549, 278) including dialkylamino derivatives (458), alkynylamino derivatives (363) and acetylenic phosphorous compounds (552). Azoles have received a great deal of attention (866, 577, 1660, 576, 2097, 578, 125, and references therein). Distinction is clear between amino and imino structures of 2-aminothiazoles (8184). Substituted phenothiazines have been studied (102). N H proton shifts are included in tabulations of hydrazone and acid hydrazide spectra (1860),various amine salts and hydrazines (96), and urethanes (207). Other systems reported are S-nitrosourethanes (1481), alkoxyamines (739), and azaphenols and quinone hydrazones (1090). =i variety of substituted ammonium ions has been studied kvith respect to inductive effects of substituents (2041). Comment is made on the broadening of various ring protons by nitrogen of thiazoles and their salts (388). Oxonium O H + is found to be -7.5 ppm from free alcohol OH and susceptible to further deshielding upon hydrogen bonding (1127). The shielding of hydroxide proton, OH-, in both dry
ammonia and in lJ2-dimethoxyethane is found to be much greater (by ca. 13 ppm) than previous estimates in aqueous solution (1880). SOSPLASAR MULTICYCLICSTRUCTURES offer a wealth of information regarding stereospecificity of coupling constants and shielding effects, as well as furnishing some very interesting problems in spectrum analysis and interpretation. S1)ecificaspects of their spectroscopy are covered elsewhere in the review. Some basic systems are listed here for which S M R spectra have been reported: bicyclo[l. 1 Olbutane (2147); bicyclo[l 1 . llpentane (2146); bicyclo [2 1 Olpentane (1787); benzvalene (2171); 2-methylene-bicyclo[2.1.1. ] hexane (1979); tetracyclo [3.3.1.0.2.8.0 4 4 nonane (1515); hexacyclo[ 5 4 1 02,6 03.l o 0 5 . 9 . 08.11]decane-4-one (1958); triamantane (2164); many tricyclic semiar omatic ethers (316). Boron-11. .A systematic study of llB spectra of borane with firqt period substituents--l\le(13X4), BXI-2, and BX YZ-amine adducts-tabulates numerous coupling constants of llB, H, F, and P, as well as shifts; the boron shifts are not additive with ligands, and a detailed discussion is presented (1556). "B shifts of tetrahedral BX4-ions are proposed to be additive in inductive and paramagnetic components of X (2029). Boron shifts and line widths for boron oxyacids are affected by p H (studies in neutral and basic solutions) (493). Evidence is presented for the formation of aquated BH2 ion in cold acidic solutions (1054). Proton .and boron SJIRdata are used to qtudy back coordination in some trivalent boron compounds (479). Metal-boron bonding has been investigated in complexes (1555, 1554) and with ~ i t manganese h rhodium (JB-RR~ -145 to 149 Hz) (1662). Transition metal poly(1-pyrazoly1)borates present a new family of chelates (1040). For some amino boranes "B ihifts were related to calculated n-electron densities (349). Other amine borane complexes, including fluoride have been studied by S l I R ( 1 ~ 2 , 1551, 772, 830). B series of B10H12 (ligand)* compounds is described (994). "13 shifts:and B-H coupling constants are reported for some triple hydrides of boron with ill and Be (1550). 1113 and proton spectra are given for PH3BH3 (1796) and fluorophosphine boranes described (1795). d reinterpretation of the llB spectrum of tetraborane, based on llB, lOB, and H spectra, as well as l l B ( H } double resonance, provides evidence for a bond between the two borons in B H groups (967). Subsequently, evidence was presented for B-B coupling via 10B decoupling (1558). Pentaborane - l l has been analyzed at 64.2 NHz, confirming previous llB assignments at 12.8 XIHz (2162). Structures originally proposed
as R3X:BH2-H-BH3 (1893) are reinterpreted as not being singly hydrogenbridged (562). The polyhedral anions B Q H ~and - ~ B11H11-2were examined by llB N M R (1128). The importance of proton and boron S M R for carborane structure analysis is emphasized in a review (1146). Dicarbaclovodecaborane 12 isomers were studied via llB h X R with proton decoupling (1658, 2093), while deuteration aided analysis of 2,4-dicarbaclovoheptaborane(7) (1581) and dicarbanonaborane(l3) (2016). Boron spectra are reported for B&&, B7C1H9, and B8C2H10systems (2017 ) and C-methylated tricarbahexaborane(7) (261). Pyrazaboles (2061), poly(1-pyrazoly1)borates (2060), and lJ4-diaza-2,5-diboracyclohexane and 1,4-diaza-2-bora cyclopentane (929) are characterized by their llB spectra. Carbon-13. The scope of I3C N l I R is illustrated in a general article (1859). Substituent additivity parameters are given to calculate chemical shifts (1375). Saturated three-to-seven membered rings containing one 0, S, or ?i have been observed (1337). The alpha-13C is most shielded in the three membered rings, as for cyclopropane 13C and for protons of three-membered ringq; however, it is noted that the carbon shifts of given methylene groups in larger rings do not behave the same as their protons. A careful analysis of methyl 13C shifts in the entire series of methyl benzenes demonstrates shielding caused by ortho methyl which is dependent on rotational conformations (2186). Ring and methoxyl carbon shifts are reported for methyl benzoates (504). The shifts of the para-carbons of phenyl phosphorous compounds are considered for determining reactivity parameters for substituents on the phosphorous (1747). The 13C shifts of biphenyl and some condensed aromatics have been determined ( 2 7 ) . A large number of substituted anisoles was studied by 13C spectra of the ring and methoxyl carbons; 2,6-disubstitution gives evidence for steric inhibition of resonance (503). The I3C shifts of various azines have been obtained directly (1217 ) and via catellites in their proton spectra (1416); in the latter case protonation was found to increase the carbon shieldings. Carbonyl 13C shieldings of aliphatic and alicyclic cyclopropylketones give some indication of the ground state configuration with the cyclopropyl ring (1593). A linear correlation is established between the lowered carbonyl shifts in some cyclic and bicyclic ketones and the n-n* transition energies; the effect is observed for single five-membered rings, but not necessarily when they are fused to another ring (1830). Carbonyl shifts have been obtained via proton spectra for benzaldehydes (1414), VOL. 40, NO. 5, APRIL 1968
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acetic acid and acetone (711). Unidentified high-field species are observed in solutions of acetic and benzoic acids in oleum solutions with high so3 concentrations (2047). The 13C shifts of alkyl cyanides, isocyanides, isocyanates, and isothiocyanates reflect similarity in bonding to carbon dioxide and carbon monoxide (1384). 13C spectra are reported and discussed for complexes of dienes with transition metal carbonyls (1218, 691, 1746). Katural abundance shifts are reported for aqueous and polycrystalline paramagnetic iron-group cyanides (461). 13C spectra of a variety of materials have been enhanced via dynamic polarization with the 2,4,6tri-t-butylphenoxy radical (1636). Nitrogen. shifts are observed directly for both 14N and 15N and indirectly by narrowing of coupled proton lines via double resonance. Study of the 14N shifts of hydroxyquinolines and some benzthiazoles shows a large change when 2-hydroxy substitution results in the oxo tautomeric form (882, 1415). Sitrogen shifts are reported and discussed for a variety of aromatic (aza and side-chain K) and aliphatic compounds (237). The 14Sshifts of primary and secondary amides are related to substituent effects on nitrogen lone-pair electrons (881). Sitrogen shifts in compounds containing oxygen cover a range of 576 ppm, attributed to dominance of paramagnetic contributions and correlated with n-n* transitions (1201). Substituent effects are reported for nitro groups of aliphatics (1664) and parasubstituted nitrobenzenes (383). 14N shifts of linear triatomic molecules and ions containing S , as well as hydracids of the latter, correlate well with calculated n-electron densities (2106,1101). Fluorine. Similarities and differences between high resolution fluorine and prpton N M R are described (2023). Fluorine shifts and couplings have been studied in a variety of aliphatic structures-perhalogenated propanes (2142); alicyclic fluorocarbons (761); alpha-fluorocarbonyls (329); fluorine vicinal to hydroxyl, acetoxyl, and methyl groups in cyclohexane derivatives (1399); fluoroalcohols (84, 799); highly fluorinated ethers (589); perfluorinated nitrogenous saturated heterocyclic compounds (1942); and QCF2CHFCl, where Q is SiMea, Sicla, P111e2, PH2, O l I e , SMe, and C1 (569). Thorough studies have been made of substituent effects on the fluorine spectra of trifluorovinyl compounds (1474, 1871). Fluorine spectra are reported for some difluoro brominated ethylenes (478), FnC=CClCF2G (G = C1, F, P(O)OXen, POCl,, and P(0)Phn) (197); cis-1,2,3-trifluoro-buta-1,3-diene (983); and hexafluoro bicyclo [2,2,0]hexa-2,5-diene (325).
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ANALYTICAL CHEMISTRY
Aromatic fluorine shifts and couplings are sensitive to ring substitution, and have received thorough study. Solvent effects are significant, being related to reaction fields (597). An equation is offered relating aromatic fluorine shifts to paramagnetic and polar contributions; Van der Waals shift is suggested to be strongly dependent on molecular geometry (322). Substituent effects on fluorine shifts of 1- and 2-fluoronaphthalenes differ from effects on physical or chemical properties of other side chains (17). The fluorine shifts of 4-substituted fluorobenzenes give evidence for steric inhibition of resonance upon incorporation of 3- and 5-methyls (496, 802). Fluorine shifts are related to pKa measurements for meta- and para-nitrogen substituents on fluorobenzene (NO, KOz, NCO, NCS, N(CF3)2, N(FC=0)2, and r\l(CF3)2CFO) (628). Substituent effects of NH3 and NOn on shifts of perfluorobenzene are additive and similar to those for monofluorobenzenes (962). Substituent effects on perfluorobiphenyls and terphenyls have been studied (324, 495). I n perfluorophenyl phosphorous compounds the meta- and para-shifts and some meta couplings correlate with urn-values of the substituents on phosphorous, but the ortho shifts do not (152). Meta and para fluorine shifts of fluorobenzene substituted with SiR3, GeR3, SnR3, and PbR3 are correlated (889). The para-fluorine shift in pentafluorophenyl boron compounds is useful to characterize dn-pr interaction (352). Shifts of fluorine alpha, beta, and gamma t o N in pyridine, quinoline, and isoquinoline are well separated and highly characteristic (353, 354). The absorption of fluorine at the 2-position in quinolines is sharpened sufficiently at -24' C to resolve H-F splittings (699). A number of N-F compounds have been reported: CF30NF2 (1894); CY,CY'bis(difluoroamine)bibenzyls (1051); PhCFzSFCR3(1444); fluorinated ureas and urethanes (120); and N-fluorimino nitrites (1286). N M R aided in confirmation of YF4+ (377). N2F3+ is postulated as NF2--SF with hindered rotation about the N--N bond (1801, 2217). Spectra are described for F3YO (691) and F 2 K C F 0 (700). Spectra of OFz, 02F2, and 03Fz are reported (1221, 1639, 1538), of which O2Fz lies ca. -865 ppm from CFC13. Bis(fluoroxy)alkanes are reported (956, 2027, 1308). Fluorine shifts in fluorosulfates, -OS02F, are studied (955) and reported (1307, 483). Among reported structures containing F, S, and K are SFSNSFZ(402, 393) ; SFsOXF2 (1800); F2S=XCN (1974); and others (1309, 792,864).
Other fluorides of note: (BFz)zBF and cis-BF2CF=CFBFz (2031) ; S P F Z H (362); SPFnR (969); SP(NCS)* F and
SP(NCS) Fz (1780); FCONCO and FzPONCO (791); methylfluorosilicates and trifluorosilyl ethers and amines (1479); and sizF6 and (SiF3)zO (1043). Liquid MoF6, WF6, and UFO give single line spectra with satellites caused 9 W 0 , and lsaW; by splitting by 97M~, their relaxation is dominated by spin rotation coupling (1768). UF6 is estimated to have a chemical shift anisotropy of 600 i 200 ppm by relaxation studies (204). The fluorine absorption pattern for solid paramagnetic UF4is attributed to six component lines, some of which are shifted upfield (evidence for hyperfine contact) and others shifted downfield-evidence for indirect coupling via partial covalent bond (1640). Shift is observed between the two nonequivalent groups of fluorine in single crystal LaF3 (1296). Dynamic polarization of some fluorinated organic materials has been investigated (1004,553). The P-F fluorines are appreciably deshielded in some fluorophosphine-zerovalent transition metal complexes (130). A Pt(I1) complex of trifluoroacetylacetone appears to have dissimilar trifluoroacetyl acetone groups, probably one bonded through oxygen and the other through carbon (777). Fluorine shifts and couplings are reported for a number of fluorovinylpentacarbonylmanganese complexes (385). Chemical shift anisotropies for fluorine were obtained in various waysfluorobenzene (molecular beam magnetic resonance) (356); chloropentafluorobenzene (NMR of solid) (1222); CHFClz ( S M R of deuterated solid) (1351). Phosphorous. Substituent additivity rules have been developed for phosphorous chemical shifts in primary phosphines (137l), tertiary phosphines (840), and o-dihydroxy-benzene derivatives of phosphoric and phosphorous acid (669). A detailed discussion of electronegativity, hydridization, and pr-dr back donation effects accompanies a report of shifts in (C6Fs), R3-,P and (C6H5)nR3--nP0compounds (652). A comparison of carefully obtained shifts in phosphonates and phosphonate ions leads to the conclusion that the great sensitivity of the alp chemical shift to the occupation of the phosphorous d orbitals renders the phosphonates a poor tool for estimating the electron donating ability of organic groups (1766). Several papers dealing with NMR are included in the published lectures of a colloquium (416). The effects of bulky substituents on triply bound phqsphorous shifts differ a little from their effects on quadruply bound phosphorous (1390). Some notable structures for which phosphorous N M R is reported are ylides, oxides, sulfides, phosphines, and phosphonium salts (1713, 1711, 1427); 2,4,6-triphenyl
phosphabenzene, with 31P a t - 178.2 ppm from &PO4 (1362); molten (CsH5P), (672); conjugation between phosphonyl and triple bonds (1430); and mobility of a methylene group attached to phosphorous (1246). Silylesters of phosphorous acid are reported (1013). Coordination of BH3 groups about P406is demonstrated (1765). 31P shifts are given for dyes in which =Phas replaced =CH(509). A regular p H dependence of phosphorous shifts in phosphorous oxyacids is discussed (1460). Spectra of K P H z (169, 1140) and K2[P(CsH5),](1014) are reported. hlesomeric cations and dications with carbon bearing three phosphorous atoms NMR (191). are characterized by Dynamic polarization of 31Pin a variety of compounds, using tri-t-butylphenoxy radical, gave positive or zero enhancement (556). 31P spectra are reported and discussed for quaternary phosphonium salts (841, 404) and aminophosphonium compounds (1022). Other salts are reported (1841, 665,1779,2155). 31Pand proton NMR data are given a variety of substituted P3N3 rings (913, 599, 680, 1226, 1840, 600, 1243, logs), and four-membered rings with phosphorous and nitrogen (825, 666). 31Pshifts are positive for (SPR2), polymers but negative for the equivalent cyclic trimer (30). Also presented are 31P spectra of a series of phospholanes (1712, 1710), dioxaphosphorinanes (IS?), and dioxaphospholenes (1714). 31P data have been listed for the following systems: CH3PF2 (1863); phosphine sulfides (1370); phosphines, hiphosphines, and biphosphine disulfides (670, 1797) ; bis-phosphino alkanes (1367, 910); Ar,PSC13-, and their AIC13 complexes (1369); chloraminated aminophosphines (390); hydrazinephosphoric acid compounds (210); and structures with P-P=X-P skeleton (1553). The shifts and couplings of phosphorous-metal complexes show general trends that are interpreted in terms of changes in phosphorous bonding and P-metal bonds. Some systems studied involved complexes with K ( 0 ) and/or M o ( 0 ) carbonyls (1734, 1245); B, Cu(I), &(I), iYi(O), Ni(II), and Hg(I1) (1897); Pt(I1) (1986); alkali metals (671); A1 (391); Sn (1842, 598) ; and Se (1368). XMR of phosphorous, as well as other appropriate nuclei, has been used to characterize a variety of inorganic structures. I n a number of halides the phosphorous shifts and, where appropriate, J p r are discussed in terms of bond character: phosphoryl halides (1519, 1487) ; thiophosphonyl halides (970) and phosphorous trihalides (1486, 1488). Solid phosphorous pentahalides show two lines even without spinning, that are attributed to PXs- and PX4+ (2162). PH2F3 and PHFl are reported,
showing temperature effects (960, 2057). Scrambling of certain halides and isocyanate structures was studied by 31P NMR (668, 667) and spectra reported for some fluorothiophosphates (622). Proton and/or fluorine XMR data often are used to characterize phosphorous compounds. I n (CF,)zSPF3C1 the directly bonded fluorines are not C (589). The equivalent a t -70' orientations of substituents on phosphorous also were examined for a number of alkyl- and aryl dialkylamino fluoro-phosphoranes and phosphines (1843). Proton spectra are reported for chloromethyl phosphine and methyl phosphinic acid (678) and (lIe2K)2PHO (757). Oxygen-17. T h e first observation of 1 7 0 in ice (HzO and D20) is reported, at 227, enrichment (2 689). l7O spectra have been used to study tautonieriqm in 0-diketones-the two enol forms of asymmetric P-diketones are distinguished (813) and kinetics are studied in 1,3-cyclohexanedione and dimedone (2200). d relationship is eytablished between 1 7 0 shift of Cr2072-and a-bonding (1216). Both 1 7 0 and '9F were observed in 02F2and 03F2(1944, 1943). Other Nuclei. Shifts of both 3jCl and 37Cl are studied in some simple organic chlorides, CI2, CI-, C101-, and C103 (1815, 1814). High reqolution 9Be spectra have been reported for a variety of compounds; line widths were 5-10 Hz and chemical shifts were nil, a shift from the reference acetate being seen ~ only for BeF4-2 ( + 2 ppm, J B e - = 33 i 2 Hz) (1164). 27Al spectra were used to study a cobalt catalyst (1861). 71Ga has been observed in symmetrical species, with shiftq more than 1300 ppm; Ga(I1) halides were shown to have the structure Ga(GaX4) (21,829). Chemical shift tensors and quadrupole coupling were measured for solid 51V in V205(812). Spectra of a number of 551In pentacarbonyl compounds have been studied in tetrahydrofuran qolution; 55Mn shifts range +lo20 to $2780 from aqueous K M n 0 4 (321). The shifts of 59C0 in paramagnetic Co301 show strong temperature dependence attributed to hyperfine interaction between observed Co3+ and electron spins of unobserved Co2' (1457). 59C0 shifts and coupling to I3C (128 Hz) are reported for aqueous K3Co(CS) (1285). 59C0 S M R has been studied for several organocobalt compounds yielding coupling constants and bond order information (1293). INDIRECT SPIN-SPIN COUPLING
General. Direct measurements of absolute values of several coupling constants have been reported. Cyclopropane (cis H-H, trans H-H, and direct C-H are +) and cyclobutane (cis H-H, trans H-H, and direct C-H are +) (1439); CH3CX (direct C-H is
+) (602); benzene (all H-H are +); fluorobenzene (all H-H and H-F are or zero), perfluorobenzene (ortho and ineta F-F are -, para F-F is +) (1938); CHFClz (F-H is +) (1342, 1351) ; and CH3F (H-F and C-H are +, C-Fis -) (174). The effects of substituents on coupling constants have received much attention, especially directly bonded C-H coupling. Simple additivity rules should not be expected when sizable interactions occur among substituents a t the site of a coupled nucleus (420, 2102). Deviations also are noted for H-H and 13CH coupling in H2C=CHX systems
+
(978).
d warning was sounded that direct bonded H-X coupling (usually H-C) is quite sensitive to the effective nuclear charge; so that a large change in JHXwith substituent does not necessarily involve a large change in s electron character at X (826). Thus, substituent electronegativity and ionicity are important factors in calculating 13C-H coupling. Evaluation of C-H coupling in halomethanes, including consideration of the halogen quadrupole coupling, demonstrates that both charge and hybridization must be considered (785, 987, 2115). Comparison of literature data shows that vicinal H-H coupling increases with electronegativity of a beta substituent, in contrast to decrease with alpha-substituent electronegativity-i.e., CH-CHX-and possibly, gamma (401). Theoretical considerations and measured values of H-C-X coupling constants and some H-X show that both couplings become inore positive with increased withdrawal of sigma electrons from X by suhtituents; 011 these grounds negative sign ir proposed for direct and geminal 1-'H coupling (642). For further discusion of this point see the section on P-H coupling. I t is predicted and denionstrated that proton-proton couplings in hydrocarbons should be somewhat proportional to the spin densities a t the nuclei in the radical fragment (516, 516, 514). Correlation is suggebted between vicinal H-H coupling constants and reactivities in certain systems (517,518). Coupling by a through-space mechanism has been invoked to explain otherwise unexpected or unuqual coupling between nuclei which are separated by many bonds, but are held very close to one another in space. Unfortunately, no theory has been developed yet. One study of the stereochemical requirements for H-F coupling b e h e e n fluorine on a benzene ring and @-hydrogen of sterically hindered ortho-alkyl groups showed a remarkable correlation between the coupling and estimated H-F separation (1516). Another very suggestive situation is a 1.1 Hz coupling VOL. 40, NO. 5, APRIL 1968
575 R
between very close OH and methine protons separated by six bonds; a weak interaction between the methine proton and unshared electrons of the oxygen may be responsible (66). Throughspace mechanism is suggested coupling in other systems for H-F through as many as six bonds (272),and long range F-F coupling in cyclic compounds (635, 649). The solvent dependence of the long range H-H coupling in acetone is not consistent with coupling by T electrons, and contribution of a through space mechanism is proposed (47’3,472). Theory. Calculation of coupling constants has received much attention. Some general theoretical developments include: a n alternant 110 description, which predicts long range couplings of alternating signs (126) ; an extension of valence-bond theory which includes triplet states in a perturbation sum (127), and another valence bond approach which handles excitation energy in a new way (549, 560). I t is shown that variations in the excitation energy should be considered before deducing hybridization, ionic character, and bond angles from W-H coupling based on the numerator of the second order perturbation energy expression for spin coupling (1812). Along the same line, several wave functions were used in calculating J H F . Even though a thorough treatment was given, including use of many excited states, the results were poor and found to be very sensitive to the wave functions employed (1080). Current mays to calculate coupling by the perturbation-variation method were analyzed, and found to be poor (1833). Rules were given to calculate matrix elements of all 1- and 2-body operators between arbitrary spin coupled functions; resemblance to the valence bond scheme is noted, but the results are completely general (427, 428). The delocalized orbital A 1 0 theory of Santry and Pople has been applied to many hydrocarbons. The original formulation (1651) was extended by those authors to handle long range coupling better (1652); proper angular dependence of 3 J H H is obtained; and although 2 J H H couplings still are calculated to be positive, they show the proper trend with angle. Generally similar results are reported by others using this approach. In one case expressions have been derived for varia(cis) with C-C bond tion of J” length in ethylene-like fragments (1509). Negative 2J couplings were obtained, but the treatments are not fully reliable (618, 2207). Calculations of VCHand lJcc were performed for several systems, giving good agreement with experiment; application to heteroatomic systems showed that this method is sensitive to substituent effects (54%). This method
576 R
ANALYTICAL CHEMISTRY
was applied to F-X, F-F, and H-F coupling of fluoromethanes and some first row fluorides, giving poor agreement for geminal couplings (1510). A formula for H-H coupling is derived by treating both the Fermi interactions and electron correlation as perturbations, and calculation performed (942). A perturbation-approach to vicinal H-H coupling in the ethane fragment, as a function of dihedral angle +, obtained dependence on cos 9 as well as on cos2+ (358). The r contributions to 5 J H H in planar hydrocarbons were calculated for conjugated polyenes, aromatic systems, and molecules with hyperconjugated methyl groups (726). There is still no satisfactory prediction of the usually negative geminal H-C-H coupling. One promising report of a negative value was considered to be somewhat ambiguous in view of the approximations made (1283). Another careful attempt was unsuccessful (917), and other calculations are reported (1719 and references above). Specific calculations of W-H coupling have been made. The alternation in sign between direct and geminal J C H in ethylene was interpreted on the basis of molecular symmetry, and it is suggested that different average excitation energy values should be used for direct and geminal calculations (2101). Proportionality between V c H and square of the bond order is obtained by a hIO approach, with the proportionality constant being a function of the general chemical nature of the carbon (2806, 2205). Correlations were studied between C-H coupling and bond order calculated by the maximum overlap orbital method (2113, 1373). W-H couplings calculated with the Dirac vector model are reported to agree with experiment (1809) H-H Coupling. I n liquid H D , the coupling is 42.94 i 0.1 Hz,t h e same as for the gas (167). Massive deuteration permitted measurement of geminal H-H coupling in some simple molecules (1261,1327). Geminal H K H coupling in amides is ca. 2.5 He (1072). A large collection of geminal H-C-H coupling constants is given and contributing factors discussed (426). The geminal coupling constant in styrene oxide shows generally linear dependence on solvent dielectric constant (1928). Vicinal H-0-C-H couplings in primary alcohols are solvent dependent and show a regular increase with electronegativity of the carbon (1467), while for X-substituted benzylamines the H-N-C-H coupling tends to decrease with increased electronegativity of the substituent R (1695). Other H?U’-C-H couplings are reported (1789, 1781). An increase is found in (J,,, Jc,,,) with heteroatom electronegaI
+
tivity for planar five-membered rings, where the cos2 9 rule also was found to be invalid for individual J,,, values; the effects are suggested to arise from contribution by the lone-pair orbitals of the heteroatom ( 7 ) . Such increased J,,, with increased electronegativity of an alpha-substituent is contrary to usual behavior. A subsequent examination of published couplings in 3-6 membered rings (73) led to the proposal that an alpha-oxygen or nitrogen contributes +2.3 Hz to vicinal and $1.8 Hz to geminal couplings anytime a pair of nonbonding orbitals is parallel to one of the involved C-H bonds. This improves reliability of the cos2 rule, as well. Nitrogen lone-pair involvement is demonstrated in long range coupling in a series of 2-pyrazolimines
+
(97).
The vicinal couplings in some cyclopentenes obeyed the cosz 9 rule reasonably well, while allylic and homoallylic couplings were fairly large (200). The vicinal couplings, J23, of both cis- and trans-3-methyl proline are virtually identical (1148). The vicinal couplings in a series of codeine isomers and derivatives were found to follow the Conroy curve closely (242). Vicinal coupling constants a t zero dihedral angle were examined in oxygen homologs of bicyclo (2 2 1) heptane derivatives (753). The following coupling constants for cyclopropane were obtained by analysis of the I3C satellites: J,,, = -4.34 (3) Hz, J,,, = +8.97 (1) Hz, and Jt,,,, = +5.58 (1) Ha (2116). Studies of aziridines (ethyleneimines) show that J,,, is consistently greater than Jc,,,, and that J,,, has the same sign as J,,, (1188, 1989, 276). I n a series of oxiranes J,,, > 2 Jim,, (1316). H-H couplings in four-membered carbocyclic rings-cyclobutanes, cyclobutanones, cyclobutenes, and cyclobutenones-are summarized extensively (663). Couplings reported for cyclobutanone: J,,, (a) = -17.5 Hz, J,,, (p) = -11.1 Hz, J,,, = $10.0 Ha,
Jt,,,, = $6.4 Hz, J24-w = + 4 . 6 Hz, J z ( - ~= ~-2.8 ~ ~ Hz ~ (1978). Similar cross-ring couplings (883) and their relative signs (1960, 1170) have been reported for cyclobutane derivatives, but apparently are very small in oxetane (1306) and derivatives (747). A series of p-lactams showed the general features J,,, > J,,,,, and large cross-ring coupling between H (3) and substituents on nitrogen (1%). Trans proton coupling is compared with bond length and bond order in a large series of cyanines, mesocyanines, and olefins (1835). The sign of J,,, in a-chloroacrylonitrile is negative, by comparison with direct J C - H(e140). .4 relatively large geminal coupling of 5 Ha is reported for the exo-methylene protons of 2-methylene-1-phenyloxazoli-
dine-4,5-dione (1391). Couplings are reported for divinyl ethers and thioethers (508), tetravinyl ethylene (1918), and beta-substituted styrene (1607). COUPLINGS THROUGH MULTIPLE DOUBLE and/or triple bonds are reported (587, 492, 1294, 1472). Various vicinal and long range couplings are reported for 1,Cbenzoquinones and related structures (1559),alkyl quinones (2107), and fulvenes (918). In cY,p,p-trimethyl styrenes the transoid homoallylic coupling is greater than the cisoid (1546). The homoallylic coupling CHs-C=C-CH is studied (380). Careful analyses of some basic aromatic or related systems are noted. Benzene: Jorlho= 7.56 Hz, Jmet,= 1.38 Hz, J,,,. = 0.68 Ha, all signs alike; differences among W-H couplings also are given (1728). J2,6 is found to be -0.13 Hz in pyridine (340) and -0.21 Hz in 3-acetyl-pyridine (2166). Para-benzoquinone: Jortho= 10.7 Hz, J,,L, = 3.2 H z , J,,,, = -1.1 H Z (1057). Pyridazine (588),quinazoline (1085) 1,2,3-benzothiadiazole (1648), and phenanthrene and derivatives (138) also have been analyzed fully. Substituent effects on ortho-coupling in monosubstituted benzenes correlate with *-electron density (701, 702) or electronegativity (539). In mono-substituted quinazolines, meia coupling is always greater across a substituted carbon (1085). The influence of resonance-contributing structures on aromatic proton coupling constants was investigated (1934), as well as solvent effects (193a). Long range coupling in condensed aromatic systems is reported between nonadjacent rings (1405, 138) as well &s between adjacent rings (1408, 1999, 1406,1609).
Long-range couplings (through four or more bonds) are not fully characterized. They appear to be stereospecific and dependent on the nature of intervening bonds. A basic reference is the review of Sternhell (1966). It is observed that the magnitudes of long range couplings are roughly proportional to the number of paths through which they can be carried (1994). Certainly observations of V , through parallel homoallylic paths, of 5.5 Hz (14S6),7 . 5 , and 11 He (546) and 6 Hz (101) would bear this out. A 5J of 6 Ha through a single homoallylic path is noteworthy (101). Long range coupling up to 2.3 Hz through five u bonds have been reported for HCCCCH (two paths) (2042, 1030) and up to 1.7 Hz via two or three parallel HCOCCH paths (1707, 234) and two parallel HBOCCH paths (2183). 5J also occurs through the carbonyl group in carboxylic acid esters (908). A six sigma bond coupling of 1.1 Hz is reported with suggestions of through space coupling (66). Relative signs of long-range couplings generally follow the pattern of negative
for even numbers of intervening bonds, and positive for odd number of bonds. Such is the case for formyl proton coupling of formate esters (909, 976) and allylic couplings (587, 815, 646, 1023). The allylic and gem methylene couplings of CHFX-CH~ have the same sign (619). Coupling through four single bonds has been seen both positive and negative (748, 12, 314, 1978, 1960, 1170). In isopropenyl acetylene all couplings but allylic are couplings positive (993). All H-H are observed and found to have same sign in 7,7-dicyanonorcaradiene (759). Novel observations of long range couplings include 4 J (331~ j , 4J ~ (2-exo-4-bridgehead) in a norborneol system (351), and 4JHXSCH (X = Gel Si) (2109). An empirical correlation is proposed between 4J and dihedral angles in the HCCCH fragment (314). Other systems in which long range couplings have been studied are rigid multicyclic systems (462, 1030, 178, 1696,2010,1613,517) through the C-K bond in amides and imides (336, 2204, 1890) ; between gem-dimethyls on tetravalent carbon bearing one or two oxygens (1606, 1450, 7 7 ) ; and others (286, 1597, 113, 941, 475, 1159, 414, 1204, 440,121, 1052,1808).
Studies of coupling in aromatic systems between ring methyl and ring pro~ v , ~ to be tons find J c H ~ ~and c to be posi~ negative (746) and J tive (1162). Substituent effects on these couplings are reported (1152, 2174). Other long range couplings between CHI and non-ortho ring protons are found in methylthianaphthenes (2001, 2002). In careful studies of substituted benzaldehydes magnitudes t o 0.1 Hz and relative signs were obtained for coupling between the formyl H and ortho, meta, and para ring hydrogen (1165, 1167), between the OH and meta-ring hydrogens, and between OCHI and ortho hydrogen (687). Couplings and their relative signs are reported among all protons of 2- and 3-thiophenethiols and their ring-methyl derivatives (769, 7 7 0 ) ; among the ring methyls and ring proton(s) of 3-substituted-(2-methyl and 2,5-dimethyl)thiophenes (7'71) ; among all protons of 2,3dimethyl thiophene, 2,3-dimethylfuran, and 3-iod0-2~5-dimethyl furan (1777); and among all but the OH proton of 2 - methyl - 5 - hydroxy - methyl furan (8043). The couplings range as low as 0.1 Hz, and insight into the coupling mechanism is gained The alpha proton of a 2-vinyl furan is coupled to ring protons (222). H-F Coupling. Both geminal and vicinal couplings in several l-fluoropyranose derivatives are found to have the same sign, believed to be positive (871). Vicinal H-F couplings are found to behave almost the same as vicinal H-H coupling as a function of
dihedral angle in structures of known geometry (2166). Such relationships were assumed in examining the conformations of some fluoroalcohols using ' J H H and a J (83). ~ ~ Long range H-F coupling through five (1516) and six (272) bonds shorn steric dependence suggestive of through space mechanism. Coupling through four single bonds is reported ( Z i ~ 4 1232). , Analysis of proton and fluorine spectra of fluorobenzene gave all H-H, H-F, direct C-H and direct C-F coupling constants (1465); signs of J H H were alike and signs of J H Fare alike (J,,,, are zero), in agreement with absolute determination ~ ~ (1938) ~ that all are positive. H-F coupling is reported also in a series of substituted tetrafluorohalodimethylfluorgenobenzenes (SO$, amine (2155) and a-fluoroisobutyraldehyde (328). 13C-H Coupling. Direct 13C-H coupling has received most attention. I n a study of solvent dependence of lJ2-dichloro fluoro ethylene, changes in shifts of H and F paralleled changes in their 13C couplings, implying similar mechanisms were involved in the change (156). Small increases in J C Hobserved for methyl chloride and trimethyl amine on going from vapor to neat liquid, and for liquid chloroform upon lowering the temperature, correlate with increased association (525). I t is noted that the Jc-H on ~electro~dependence ~ of methyl ~ ~ negativity of the atom t o which it is attached is regular for each row of the periodic table, and varies from one row to the next. This is attributed to anticipated variations in bond hybridization (524). The geminal C=CH couplings of some acetylenic derivatives of elements in periods IVALI,VA, and VIA are more sensitive to changes than are the direct couplings, with no evident relationship t o chemical shift (1914). Correlation is noted between laC-H and BSi-H coupling constants and the stretching force constants for these bonds (289, 1064). Nonadditivity of JCH for polysubstituted methanes is handled by relating the coupling to substituent electronegativity and bond length (1235). The CH coupling in the formyl group, X-CHO, is related to electronegativity of X (826) and t o substituent effects of X on methane J c H (877).
Practical use of direct C H coupling in cyclic and heterocyclic series is proposed relating to bond angles and inductive effects (1215). ' J C H correlates with Hammett u parameters of substituents on fluorobenzene, but regularities are not found for ' J C F (1464). Direct 13C-H coupling3 are reported for methoxide ion (130.8 Hz), formate ion (194.8 Hz) (875) and carbonium ions (1573). The direct C H coupling of the methylene protons in cyclopropane and some heterocyclic threeVOL. 40, NO. 5, APRIL 1968
* 577 R
membered rings is consistently ca. 33 Hz less than for the corresponding open chain structure (1693). I n a rather broad study, it is found that J 1 3 C C C R and J l a C H vary togetheri.e., J,,, increases from neeative to positive values as J d l r e o t increases. This behavior is predicted theoretically (1810). The long range l3C-H, cou= +1.0 Hz, plings in benzene are JCCH JCCCH = +7.4 Hz, J C C C C H = -1.1 HZ (2124). Consistent is the report that for l13,5-trichlorobenzene 3JHCCH (711), ' J c H , and 3 J C C C H all have the same sign. I n vinylene carbonate J C H , J c C H , and JHCCH all have the same sign (1346). A variable temperature study of propionaldehyde and its oxime o-methyl ether gave support to the prediction that trans J C C H is greater than gauche JCCCH (1078). I3C--H couplings were used to study structures of some small strained rings (269, 1649, 1373), and in thiazoles (2095,,9096). N-H Coupling. Measurement of relative signs of H-H and K-H couplings in ls.V-formamide and methyl formamides gives V I S X - H - , 2 J ~ ~ ~ ~ 'JWCH~-
i
4JHC(0)NCHs-
3JHh-C(0)H+
1
3JHKCHa+
(644). It is noted in this
article that the relative signs of N coupling, after correction for sign of magnetogyric ratio (negative for IJ.V, positive for I4R, J3C, H), follow the essentially same behavior as do couplings. I n quinoline-'% and its ethiodide the couplings to H(2) and H(3) have the same sign, but the signs are unlike for the S-oxide; coupling to H(4) or H(8) also ryas seen (2044). I4N-H coupling constants to the vinyl protons of trimethyl vinyl ammonium bromide (1570) all have the same sign, and magnitudes in order Jtrana > J,,, > J,,,; the same ordering is seen in quaternary enammonium salts (1242). I n ethyl isonitrile the geminal and vicinal I4K-H couplings are opposite in sign (1366). A compilation of 1%-H couplings includes both short and long range values (236). I n lSS-oximes the geminal ' J X C Hcouplings are -15 HZ for protons in anti positions and -3 H z for cis; the difference is attributed to nitrogen lone pair effects, and the large anticoupling would account for 14N-broadening of the lines of protons alpha to nitrogen in heterocycles (1121). Direct and long range 15i\j-H couplings are reported for p j ~ i n i i d i n e - ~ % and ~ some derivatives (17'71). Direct W-H couplings have been measured for X-X-H compounds (X = Si, Ge, Sn) in attempts to deduce (p-d)r character in the X-3' bond; no real evidence is found (1715, 1718). I n alkyl pyridinium salts, 14K-H coupling is observable only to beta protons (182). 'Jllh-CH = 1.38 (8) Hz for acetonitrile, by spin-echo technique (211). Studies of long-range l4N-H coupling in alkyl
578 R
ANALYTICAL CHEMISTRY
ammonium salts include discussion of JZ~AI-E = 6.34 HZ (1575). JZ~AI-H = 14N relaxation as observed by broaden44 HZ in ( C H Z ) ~ NAlBHa . (190). An ing or loss of structure in the proton empirical equation relates direct 29Si-H spectra (766,1259,1092,1238). coupling in H3Si-SiHzX to values for P-H Coupling is quite sensitive to SiHzX, SiHa, and SiH3-CH2X (2615). the electronic character of the phosPair-wise substituent effects are given phorous. An interesting set of reports for direct Si-H coupling in silanes (194). on phosphines illustrates this behavior. Si-H coupling is discussed for the I n the methyl phosphines, l J P H and purported structure (CH3)3K:SiH3-'JPCH are shown to have like signs. CFzCHFs (424). One interpretation of the change with Both 29 Si-H and W-H couplings substituent, based on comparison with are reported for some silyl esters (569), parallel behavior in alkyl ammonium some A' - halohexamethyldisilazanes and alkyl tin systems, states that a (lo?), and 1,1,3,3-tetramethyl-l,34negative sign is implied (64%'). On the silacyclopentene (730). d triple mixed other hand, these couplings were shown anhydride, SiH3PH2BH3exhibits many 8 to have the same sign as 3 J p c ~ nand couplings in the proton spectrum: H-Si-P-H, H-Si-P, H-Si, H-P, 'JHPCH, where the latter value is expected to be positive (1378). A later and H-P-B-H (530). in H (CH3)3P, (CH3)2PhP, study of J ~ C I n Cd(CH2CHZ)z the JCd--CH2 has (CH,)Ph2P, and (CH3O)aP showed that sign opposite to JCd-CHa, while for Sethe signs of all but the latter change (CH&H3)2 and Te(CH?CH3)?the metalupon complexation with aluminum CHZ and metal -CH3 couplings have like sign (271). The 77Se-H couplings alkyl (446). Finally, the absolute signs of the couplings (except phenyl) in in chromium tricarbonyl complexes of (CH3)zPhP and in (CH3)2PhPH+Brselenophene and of 2,5-dimethyl selenohave been obtained by comparison with phene are found, surprisingly, to be the ((positive) ~ ) ~ - J,1 a c - H (1330). On going same as for the uncomplexed comfrom phosphine to quaternary the signs pounds-coupling to both the ring pro- ~to +), 2 J p c H (+ to -) were l J ~ (tons and methyl protons is reported with values l J p H = +525 Hz, 2 J ~ ~ H (1564). I n a proton N l l R study of = +4 He, and a J H C p H = f5.5 Hz for benzyltin derivatives J8,- C-H could the quaternary. Combined results, not be interpreted on the basis of Sn then, imply that l J p - H must be positive s-electron density alone; 13C-H cou(same sign as J l 8 C - E ) in the uncomplexed pling also was reported (2090). J B ~ - H phosphines. values are reported for 1,Z-bis(trimethOther reports of relative signs for yltin) benzene and related compounds trivalent and/or pentavalent P-H (615). 199Hg-H coupling through four coupling through two to four bonds, sigma bonds is found in neopentyl mersome of which may be double, find ' J curic chlorides (1916). is related to and 3J to have like sign [in one case substituents and conformations in shown to have the same sign as JECCHseveral trialkyl mercuric chlorides (548)l while signs of the rather small ( I l l y ) , and reported for mercury ace4 J P H coupling are not consistent (551, tate (1921). lg9Hg-H coupling con2004, 1915, 1203). Long range P-H stants are tabulated for a variety of couplings are strongly dependent on organomercury compounds (1205). geometry, as well as coordination and Pb-H coupling occurs to all protons of substituent electronegativity and lone (p-CH3-C6H4)4Pb and (p-CH3-C6H4)6pair orientation (304, 749, 750, 455, Pbs (1125). In [KizH(CO)ia]- JH'83rV 1094, 1216). J p H values in most ethyl= 41.9 HZ and J ~ - \ y - 1 3 ~ = 2.6 HZ enic systems follow the H C C H behavior (911). J 1 O a R h - H was studied in a number of rhodium-methyl compounds Jlram > Jcw > J g e , (1203, 161, 1104, COU1394, 1247, 1823, 163). P-H (732). pling occurs through as many as nine F-F Coupling. M e t a F-F coubonds in systems with multiple double pling in substituted benzenes correlate bonds (especially aromatic) (1114, 1113, well with n-electron donating or with1075, 835). Some relatively unusual drawing properties of the substituent, systems or couplings reported are 12 Hz to ,- - 10 HZ varying from 3 J p C p H 2 = 4.3 Hz in a protonated cation (962, 1614, 6). Other references to having three phosphorous atoms bonded F-F couplings in rings are made in to a single carbon (191); J P H= 138 Hz articles dealing with shifts as well (see in KPH2 (169, 1140); 3 J ~ - r ~ o -section ~ C - on ~ fluorine shift). Study of and V p - 4 , - h-- c- c- H in Co (111) comperfluoromethylcyclohexane and the 4-H plexes (826). A proton-proton cousubstituted isomers gave for F-F coupling VH-C- 0- p- C- H has been detected plings 3J,,,,, 0-3 Hz, 3J,,uche -14 Ha, 4J,q-,q -9 Hz, 4JBx-eq -1 Ha, and (643)* Other H-X Coupling. llB-H 4JBx--ax -27 Hz (1615). Compounds coupliiig is reported for (CD,O)?BH from addition of fluorine to indenes and (162.0 Hz) (213); B(OCH3)s (101 Hz) couplings acenaphthenes gave F-F (1.478); and C R 3 X H 2 .BF3 and (CH3)2showing geometry dependence similar to K H B F (long range B-CH3 coupling H-H and H-F couplings (1443). (831). I n LiAl(CH3)4 observed) Substituent effects differ for J,,, and
-+
positive and 'Jl8Hg-C-H negative for J,,,,,, in 1,2-difluoro ethylenes (131), dimethyl mercury (1349). I n contrast but for 1,l-difluoro ethylenes J,,, corto above results, where the reduced ielates well with their mean chemical direct X-13C couplings are positive shift (1755). (Similar studies covered and reduced geminal X-C-H coushifts as well-see section of fluorine plings negative, the opposite is reported shifts.) p,p- and a,p-difluorostyrenes for RlezSe, Me2Se2, Me8Se+I-, h!IezTe, are repoited (1870). In dimethoxyand MeaTe+I- (1332). A P-C=P is tetrafluoro Dewar benzenes JFC-CF coupling of 47 i 7 Hz is reported (192). only 4.2 Hz (343). In fluorimines trans A strong P-P coupling is noted beF-F couplings are found to be larger tween non-trans phosphorous ligands in than cis (557). Vicinal J F F lies in the range 1.5 to 4.4 Hz for several C F ~ C F Z - a rhodium complex (1853). Copper (I) trialkyl phosphite complexes display Se-compounds (2f32). I n cis fluorolarge P-63Cu and P-Wu coupling titanate complexes, TiF4.2D, J F F values (1118). J 1 7 0 - 3 5 ~ 1 = 86 Hz in Clodrange from 34 to 49 Hz (558). ion, but is not seen in C103- (26). LOXG RANGEF-F COUPLISGSreported in some cyclic systems are attributed to through-space mechanisms; KINETIC PROCESSES 'JF-c-c-C-C-F -25 HZ (119),' J F C C = C C F General. An excellent coverage of (635), and through five single bonds theoretical aspects and applications is 'JFCCCCF = 43 Hz (649). I n some agiven in a chapter "Chemical R a t e and p-fluoro pentafluorostyrenes, the Processes and Magnetic Resonance" para-fluorine generally is coupled to (1047). Related is a chapter on " X N R a-fluorine, and in one case coupling to a Measurements of Reaction Velocities 6-fluorine \va$ observed ( ' J F r ) (323). and Equilibrium Constants as a FuncFive bond F-F coupling is observed for tion of Temperature" (1735). A review F C K K C F (519) and in bistrifluoroarticle covers association, dissociation, methylamino sulfur compounds (590). and exchange phenomena in solution Other. Direct 13C-F couplings (1018). Experimental support for the are reported for some fluorinated soundness of kinetic measurement by cyclopropenes and cyclopropanes (2035) line shape analysis is obtained in a and for some broniofluoroethylenes study of internal rotations in amide by (1751). In HBF?, the B F coupling is rate of equilibration from one isomer opposite in sign to the B H and HF and the line shape a t equilibrium (1385). couplings (2238). The III3-F coupling K M R , thermal maximum, and scavengin XgBFd changed from h1.1 Hz to ing techniques all gave good agreement +0.4 Hz on going from water to acetowith one another in measuring rates of nitrile as yolvent (782) J " 0 - F = 39 dehydration of acetaldehyde hydrate i 6Hz in acetyl fluoride ('70 shift is -374 ppm froin external H P O ) (175.2). (614) Some applications of line broadening or narrowing and shifting by JNI' = 135.5 Hz in ONF3 (139). kinetic processes are discussed (463). Relative coupling signs for (CF3)2PSCF8 and (CF3),PF, based on ~ J P F The line-shape expression for chemical exchange is derived from a rigorous negative, are , 3 J p F 3JF~-,and density matrix theory and found to be 'JFF'' (450). I n compounds SiF3(SiF2), the same as that of Gutowsky and -BF2 coupling is observed for Si-F, Saika (225). The Gutowsky-Holm F-Si-Si-F, and B-F (2032). Platequation for exchange between two inum complexes with perfluoroethylene equally populated sites has been transand triphenyl phosphine display couformed to dimensionless parameters plings 2 J p , F , ' J P F , and 3 J F F (887). Simi(1523). Exchange rate for the protons larly, P-F coupling is observed in coof ammonium ion at low p H has been balt complexes with CzF6or n-C3F7 and studied via field dependence of the protriphenylphosphine (2058). Other unton relaxation; the exchange affects usual coupling constants reported inrelaxation when ( W E - W X ) exchange clude 73Ge-F, 49Ti-F (467), IQ5Ptrate, and can be measured a t low fields C-F, and '''Pt-C=C--F (386). (static or rotating frame) (1689, 166). The direct l3C--I3C coupling in The theory of Kaplan and Alexander acetic acid is $57.6 Hz, based on for exchange has been applied to ex(821). In acepositive direct W-H change among three species with any tonitrile-'%, 2J13CC1SY = +3.0 Hz, 3 J ~ 6 h ~=~ H 1.8 Hz, ~ J U C - I S N = - 17.5 number of coupled spin-'/* nuclei; it was used in a thorough study of hinHz, and ' J l 3 C C H = -10.0 Hz relative dered rotation in halogenated fluoro136 0 Hz (note that reto 'J13C-H = ethanes via their fluorine spectra (1544). duced couplings involving 15S would A theoretical expression is derived for have opposite sign) (1329). I n tetrachemical shifts as a function of associamethyl silane ' J i a c - z s s I is negative and tion constants in monomer-dimer (or z J ~ ~ sis+ positive c - ~ based on ' J l 3 C - H trimer) and chain equilibria, with applipositive-reduced couplings of %i cation to some alcohols (179). would have opposite signs (1347, 1348, Spin echo techniques allow measure468, 469). I n the same way, ' J 1 5 9 S n - I ~ is negative and z J 1 5 S S ~ ~ C His positive for ment of fast exchange processes. Reference is made to these in the section on methyltin halides (1331), 1J119Hg-lac is I
+
+,
-
+
pulse techniques. Pulse and high resolution N M R methods are examined and compared critically for precision and methods of minimizing systematic errors (34). Pulse methods have been used to study the rearrangement of bulvalene and its silver complexes (35), and perfluorocyclohexane (868). The effect of intermediate states on kinetically broadened XMR lines is considered in a study of the hydration of acetaldehyde (18). It is shown t h s t an exchange-narrowed line contains a temperature-dependent component uninfluenced by exchange; this was considered in analysis of conformational equilibria of some six- and seven-membered heterocycles (1838). The study of saturated-ring inversion processes by ?;AIR is aided by use of gem difluoro derivatives (1772). S M R studies are included in a review of properties of compounds having diamond skeleton, including internally exchanging bonds (2210). Proton K M R can be used to determine the number of solvent molecules taking part in exchange between solute and solvent--e.g., amines in proton solvents-by measuring exchange rate for solute and solvent separately (845). Changes in 13Csatellite structure can be used to measure proton abstraction CH3SOCH2rates-e.g., CH3SOCH3 (266). It should be noted that broadening of satellite spectra can be caused by shortened relaxation time of the splitting nucleus as well as by exchange of the observed group from one nucleus to another (873, 681). Positive Overhauser enhancement for t-butyl protons of tri-t-butyl phenol in the presence of its phenoxy1 radical is associated with the proton exchange and scalar coupling with the electron (554). .%cetyl exchange between acetic acid and acetic anhydride has been studied by S M R ( 1879). N M R is quite useful for studying rates and equilibria of hydration of carbonyls, being more accurate than the ultraviolet method (963). Hydration studies are reported for pyruvic acid (838), "8-azapurines" (302), and mono- and dihydrated pteridines (25). spectra have proven to be quite useful for exchange studies. Ketone and aldehyde oxygen exchange with water is attributed t o hydration (833, 834). For acetylacetone-water systems the keto oxygen exchanges faster with water than does the enol oxygen (1313). Kinetics of 170exchange with wator have been determined for periodate (1617) and tellurate (1311). Exchange. A review on exchange equilibria a n d analysis of mixtures of unstable compounds points out t h e importance of K M R measurements, with examples of inorganic systems (2085). Mathematical treatment of scrambling of two kinds of substituents
+
VOL. 40, NO. 5, APRIL 1968
579 R
between two central moieties is discussed (2086). Shifts of end groups on “long chains” (such as dimethyl polysulfates) are very sensitive to the exchange of atoms in the central region (2084, 2083). Poly oxymethylene (formaldehyde polymers) have been studied in aqueous solution (999) and as the chloro- or dimethylamino-terminated structures (1461). Other equilibria studied by proton N M R include trimeric-tetrameric ring structures of dimethyl-germanium oxide (1459) and equilibrium of complexation of BFs in ethyl ethercyclic ether systems (1571). Exchange between bridging and terminal positions in aluminum alkyl has been studied (1709). ”I3 spectra were used to study boratepolyborate equilibria in aqueous solution (1465). ’Li and proton spectra have been used to obtain kinetic data for alkyl lithium-other metallate exchange reactions (2161, 1866, 1867, 1868). Molten methyl ammonium chlorides have been studied for both H and CH3 exchange; aniline and dimethylanilin exhibit exchange of methyl and hydrogen, but not phenyl (951). Amides. Conformational studies of amides continue to be a popular subject. Konplanar structure has been of the suggested-nonequivalence benzyl methylene protons in s-benzylx-(orthomethy1)phenyl acetamide is attributed to possible slow inversion of the nitrogen (1904), while for dimethylformamide (DAIF) a decrease in the trans formyl-methyl proton coupling upon lowering the temperature is attributed to existence of a more nonplanar structure a t higher temperatures (2070). -4 study of barriers to rotation in
x,r;-dimethyl amides and related structures in D M F solution indicates that the rotational barriers decrease in the amidiorder thioamides > amides nium ion > amidine, with J l z C H of the methyl protons correlating directly with the magnitudes of these barriers (1545). x-vinyl substitution lowers the rotational barrier (765). D J l F rotation has been re-examined (423). Barriers to rotation are affected by association with other molecules as well. The D M F barrier of 6.2 kcal/mole in tetrachloroethane is raised to 14.5 kcal/mole upon complexation with BF3, while BClr forms two types of complex (809). Solvent effects were used to estimate s-cis to s-trans conformation ratios in eleven- and thirteen-membered r-methyl lactain rings (1475). Solvent effects on hindered rotation in N,Ndialkyl amides have been studied (2145). Bulky s-substituents affect cis-trans rotational isomer ratio and molecular conformation, especially in cases of anilides with 2,6-disubstitution (1111, 2126), a free energy of activation of
-
580 R
ANALYTICAL CHEMISTRY
ca. 31 kcal/mole being estimated in one case (1956). In x-methyl and x-ethyl formanilide (245) and in x-methyl acetanilide (1618) the phenyl and carbonyl oxygen are 95% trans to one another. Rotational isomers of s-alkyl thioamides can be separated, their rotation activation energies being in the range 25-27 kcal/mole (1582, $108). Hindered rotation is observed in N,Ndimethyl carbamates (1301) and in r;-nitroamides and x-nitrocarbamates (2141) a t low temperatures. Evidence is found for hindered rotation of alkalenebisamides but not for alkalene biscarbamates (129). Hindered rotation occurs about the C--N single bond of x’-aryl-s,s-dimethylformamidines, ilrN=CH-N(CH3)2 (175). OTHERHINDERED ROTATIOM IXVOLVING XITROGEN have been studied, including syn-anti isomerization of imines, oxime ethers, and haloimines (452), and ethyl nitrites (110). The CF2group of (CF8)2CF-?;=CF2 collapses to a single line a t higher temperature.. due to rotation about the C=N bond (AH* = 11.0 kcal/mole) (1567). Estimates are made of the rotational barrier about the =C-N bonds of enamines and =N-N bonds of hydrazones (1585). Para-nitroso-dimethyl-aniline is shown to have a barrier of 14.9 kcal/bond (1158). mole about the C-SO Hindered rotation about the K-X bond has been studied for tetrafluorohydrazine below -145’ C (415), tetrahydropyridazine (1157), diacyl hydrazineq (195), and vapor-phase dimethylnitrosamine (2 kcal/mole less than in CC14 solution) (894). Other studies characterize hindered rotation about the S--9 bond in s,vdimethyltrichloromethanesulfinamide (lo%$)and about the B--r\’ bonds of aminoborons (1945, 1547).
Nitrogen Inversion. Inversion of aziridines has received some attention with regard t o effects of ?;-S and X-P (72), and N-C(0)R (much (69). Carefully faster than N-R) dried 2,2,3,3-tetramethyl aziridine has E, = 11-11.9 kcal/mole for ?J-H and (124). 14.3-15.0 kcal/mole for S-D The nitrogen inversion of N-benzyl-0, wiimethylhydroxylamine is found to be related inversely to solvent dielectric constant (856). Hindered nitrogen inversion is found in a series of dihydroquinolones (1948). Phosphorous inversion is observed in phosphines, the activation energy being 26 kcal/mole for 1,2 - dimethyl - 1,2 - bis(2,4,6-trideuteriophenyl) diphosphine (1198). Slow sulfur inversion is observed for a sulfide complexed to Pt ( 3 ) . Multiple Rate Processes. Consecutive inversion of two adjacent nitrogens is proposed for 2,3-diazabicyclo [2 2 11 heptane and bicyclo [2.2 21 octane compounds (50, 37).
Related is a study of ring inversion and hindered rotation in r;.,x‘-dimethyl tetrahydropyridazines (49). More than one “slow’” kinetic processe? can be seen in many amidecontaining systems. Ortho substituted anilide? have shown simultaneous processes (1898). Slow rotation is observed about both the carbonyl-S and carbonyl-aryl bonds of ortho- and meta substituted benzamides (1902, 1900, 1906). Ring inversion and amide rotation have been observed in a number of cases (1672, 268, 308, 1671, 1673). CONFORMATION AND CONFIGURATION
Conformational Analysis generally is based on correlation of chemical shifts with local environment and/or dihedral angle dependence of vicinal coupling constants. Often, interconversion among conformers is examined kinetically, especially for flexible ring compounds or moderately hindered rotation. Many of the general aspects are discussed elqewhere in the review. This section will cover other work dealing directly with conformational analysis and characterization. At infinite dilution in CC14 alcohols are assumed to be monomeric; the rate a t which an OH shift approaches its infinite dilution value, a t low concentration, is proportional to its monomer-dimer association constants and, therefore, reflects its qteric environment (1590). Solvent effects on shifts of sterically hindered alcohols are useful to determine configuration ( I 1 71). Conformational preference of OH in cyclohexanols is reflected by vicinal HCOH coupling conqtant or OH shift in DMSO (1692. 2066). But the behavior of ditert-butyl carbinol HCOH coupling represent. posqible conflict in interpretation (1608). The OH shifts of oximes in DMSO qolution can be used to assign stereochemiqtry (1130). The shifts of lacbearing OR is sensitive to conformation of the oxygen function (296). The protons of trimethylsilyl ethers are more shielded when the group is axial than when equatorial (1062). The shifts of neighboring protons are affected by confipuration of carboxylic acid groups (1532). A quantitative method for ring conformation analysis is offered by the H ( l ) shift of 1,2-dibromo cyclohexanes ( I 759).
Long-range shielding by phenyl groups is used to establish configuration of carbomethoxy groups in aryl cyclopropane carboxylates (1177), and gives specific shielding effects a t protons 6, 7, or 8 bonds away, but not 5 and 9 bondq, in some open-chains containing double bond (1638). Long-range deshielding of 0.7 to 1.0 ppm is caused by lactam carbonyl in a peri relation (660). Line widths of axial methyls are
greater than for equatorial methyls on cyclohexane rings, due to long range coupling (1892, 1891). Similar behavior is observed for methylene protons of exocyclic epoxides (532). Qualitative determination of nonchair and distorted-chair conformation. of sixmembered rings can he made on the basis of the ratio of average trans to cis vicinal proton coupling constants (1193). The geminal H-C-H coupling correlates with trans- or cis-fused rings in 8-oxa-I-azabicyclo [4.3.0] nonanes (442). Conformation of 1,3butadienes may be deduced from proton-proton coupling constants (242). A model is proposed for deducing conformation in acyclic systems on the basis of vicinal proton-proton coupling (1937). Correlation is found between dipole nioiiients and vicinal protonproton coupling in certain trans-1 ,2disubstituted rings ( 4 1 ) . Overcrowding in a-alkyl-ortho-nitroanilines is reflected in shift changes of the ring protons due to loss of coplanaiity between the ring and the nitro gioup (1694). E X D O R spectra demonstrate hindered rotation about the ring-CH2 bond of ortlzoRSCH2-CsH4--C‘(C6Hj)L at low temperatuie (996). Enantiomers have been resolved “directly” in both fluorine (1641) and proton (306, 1042) spectra. Optically active solvents of the sort .Ir-CH(R)X weie used, nhere X wab O H or SH2 and R was CH3 or isopropyl. Coniplexation between solvent and solute is presumed to form diastereomeric complexes ; dilution of these complexes with inert solvent species reduces shifts between enantiomers. I n addition, the solvent need not be optically pure to give observable effects. Another effective method is to form actual derivatives of the enantiomers with an optically active structure to give formal diastereoisomers (1687). This technique was applied to determination of optical purity of e-deuterio benzyl amine (767) and replacement of one CHI by CDS in isopiopanol (1688). Magnetic Nonequivalence is reviewed with reyiect to chemical shift difference between protons or methyls/attached to the ianie carbon (1403). theoretical treatment for geminal protons confir ins general rules that are found to be valid (489). The piobleiii of separating intrinsic nonequivalence from effects of conformational populations remains (2076, 1936, 1686). However, directions for future stud!- may be indicated by obsei vations of coupling differences that are not attributable to simple conformational effects-the direct W-H coupling differs for nonequivalent geminal piotonq of an ethoxy group (1722) and H-F couplings differ for the nonequiralent methylene protons in a CFI-CH~ group (703). .In unusual temperature effect reported is
increased chemical shift between nonequivalent methylene protons, as temperature is raised, in 2,3,5-trimethyl2,3,5-tricyanohexane (1927). Observation of greater nonequivalence for the methylene protons farther from the center of asymmetry in CH3CH20CHC1CH2CH3 is attributed to amplification of asymmetry by the oxygen lone pair (301). Yonequivalence of vicinal protons on an epoxide ring is caused by phenyl attached to an asymmetric center as much as six bonds away (1044). The allenic system can resemble tetrahedral carbon in supporting magnetic nonequivalence for associated methylene groups (2401, 1402). Orthosubstituted phenyl rings attached to a planar trivalent atom can cause nonequivalence a t positions farther on, presumably as a result of strongly hindered ring rotation a t lower temperatures. Such nonequivalence is reported for the methylene protons of N-CH2R of benzaniides (1905, 154, 155), methylene in substituents on fully substituted planar nitrogen bearing an ortho-substituted phenyl (1901, 1876) and ethyl methylene protons of the enol form of ethyl 2-(2,4-dinitrophenyl) acetoacetate (872). Proton nonequivalence has been investigated in a variety of organonitrogen and organophosphorous compounds (1899). The spectra of erythroand threo-2-butanol-3-d, as well as the undeuterated alcohol, have been analyzed and solvent effects examined ( 1020). Cyclic Structures. Cyclobutane derivatives are shown t o be noiiplanar by examination of proton-proton coupling (angle estimated a t 9-1 l o ) (1304), by temperature dependence of geminal fluorine-fluorine shifts (1199), and temperature dependence of vicinal H-F coupling (1200). The fluorine studies also included a cyclobutene and cyclobutanone, where lack of temperature dependence implied nearly planar stiuctuies. Five-membered ring. containing Group V atoms and -CH2-CH2have been compared for effects of nonplanarity, rapid inversion, and effects on ring proton equivalence (689). The S-0 group is proposed to be predominantly axial in the cyclic sulfites of 2,4-pentanediol (1592). Six-membered rings continue to be studied extensively. Conformational free energies are reported for the vinyl group (1591), the formyl group (297) and nitro group (2049, 698),all of which are preferably equatorial. The space demand of the lone pair of electrons on nitrogen is reported to be less than for attached hydrogen in cis-decahydroquinoline (231) but apparently greater in piperidine (1196, 1197). Significantly smaller lone-pair size relative to bonded H is claimed for oxygens to account for observation of axial tert-butyl groups
in cis-2-alkyl-5-t- butyl- 1,3-dioxolanes, compared to the usual equatorial placement in cyclohexanes (580). Similar argument is applied to the nitrogen lone-pair electrons of l-t-butyl-3methyl-4-piperidone (273). Two review articles cover methods and results for conformational analysis of cyclohexane ring systems by S X R , including kinetic and equilibrium studies (579, 638). Methods and interpretation of kinetic data for ring inversion of cyclohexane are dipcussed (892). A high resolution proton S M R study of dli-cyclohexane inversion obtained a AS* value that does not agree with earlier spin-echo results (65). -1niisunderstanding in the interpretation of an earlier cyclohexane inversion study was corrected (35). . Pure (or nearly pure) equatorial chloro- and trideuteromethoxy-cyclohexane have been isolated by low temperature crystallization, and observed as such in solution a t -150” C (where conformer half-life is several hours) (1036). Inversion and conformations of 1,l-difluorocyclohexane and Some derivatives have been studied via fluorine Y l I R (1947). Conformationq and inversions have been studied in other substituted cyclohexane systems : cyclohexyl and heteronuclear six-niembered rings (171); 1,1,4,4-tetramethylcyclohexane and derivatives (1756, 1507) and the corresponding piperazinium dichloride (13); acetoxy-, tosyloxyand methyl-cyclohexanes (346); P-chlorocyclohexanols (214); and cis-1,4bromochlorocyclohexane (217 9 ) . Inversion of 3,3,6,6-tetraniethyl-l,2,4,5tetraoxane (1508) and 1,3-dioxane (51) has been studied. Attempts have been made to evaluate the “anonieric effect” in 2-halogeno-tetrahydropyrans, where dipolar interactions may cause halogen to be axial (232!,44). Kinetic studies are reported also for morpholine and piperazine derivatives (893), hexahydropyrimidines and hexahydrotiiazines (1763, 624, 1241, 1762), and perfluorox-fluoropiperidine and -morpholine (1229). I n s-acyl piperidines and similar systems ring protons cis to the carbonyl oxygen are deshielded by it if equatorial and shielded if axial (1610). Conformational free energy difference has been measured for the oxide function of thiane-1-oxide (1196). .hisotropy of the S-0 bond is analogous to acetylene rather than to carbonyl, based on study of 1,4-oxathian-S-oxide derivatives (298). Temperatures as low as - 170” C were required to study the ring inversion of de-cyclohexene, for which AF* = 5.3 kcal’mole, AH* = 5.3 kcal/mole (67), while inversion AF* of 5.93 kcal/mole mas found for 4-bromo-cyclohexene, yielding AH* = 6.1 kcal/mole and AS* = 1.4 eu (1035). Conformational studies, including kinetics, have been reported for cycloVOL. 40, NO. 5, APRIL 1968
581 R
hexanone and simple derivatives (235,
=C-C(0)N (1903); N-B (150,2046), (CeHb),PC-C (O)CH,, (CeHs),PCconformational studies of dihydropy(CH3)-C(0)0CH3 (E8= 14 kcal/mole) rimidine-diones (347, 1790) and dihy(177) ; substituted cyclopropanes (851, drocycloheximides (1050, 1049), and ,241, 476). Rotation about “double 4-substituted cyclohexenones (186). bonds” is claimed (1098, 1110, 1011). Ring inversion has been observed in Rotational conformation has been in1,4-dioxene derivatives (1633), and cisvestigated for biphenyl (1433) and 5,lO-thianthrenedioxide (1682). Anomvarious bipyridyls (337, 320, 1951 , alies noted in some trans-9-amino-101952). DL-threonine and DL-valine in D20 solution both appear to exist as decahydronaphthols are attributed to two long-lived rotational conformers a t steric effects (1659). Inversion of heterocyclic analogues of metacycloroom temperature (90). Possibly rephane has been studied (764). lated are results for phenylalanine, Low temperature behavior and proton glycine, and alanine (344). Energy difexchange of 1,1,4,4-tetramethy1-6,7-ben- ferences between gauche and trans conformers of many 1-substituted 3,3zocycloheptene allowed observation of dimethylbutanes imply relative “sizes” racemic boat and chair forms, with boat chair interconversion and chair racemiof groups that differ substantially from those estimated in cyclohexane systems zation each being studied kinetically (844). Similar considerations were (2144). Tautomers. Enolic OH chemical given other benzocycloheptanes (295) shifts and peak widths of p-diketones and benzo-di- and tri-thia-cycloheptanes depend on t h e nature of substituents, (1068, 1069). Inversion studies are reported also for 7,12-dihydropleiadenes and the shifts correlate with formation constants of metal chelates (1207, 1208, 1209, 1210); cycloheptatrienes (1194, 2037); azepines and diaze(1272). Enol OH shifts a t infinite dilution in pyridine are linear with pK, pines (1384); and benzodiazepinones (1271). Cyclooctane studies show pref(1151). The hydroxymethylene ketone aldo enol equilibrium was investigated erence for boat-chair or twist boat-chair conformation (1616, 70, 71). Kinetics in a number of compounds (484, 760). are studied for inversion of 3,5,7-cycloEnol forms dominate in some p-thioketones, with evidence for another tautooctatrienone (758) and eight-membered rings containing two nitrogen and two mer at higher temperature (1134). A sulfur (or selenium) atoms (1240). Slow number of @-diketone diimine Schiff bases and their diamagnetic metal inversion of a ring formed by a -Cchelates have been examined, with relaC-C-C-0bridge from C(1) to tively little spectral changes noted upon C(8) of 2 - substituted - 3 - isopropyl replacing two ligand protons by metal naphthalene causes observable nonequiv(1323). valence of the isopropyl methyl groups The quinonoid form of ortho-([IjN]( E , for inversion is 14 kcal/mole) (422). For cis-decalin inversion AF* -13 methy1acetamidoxy)phenol was rekcal/mole (1037). Inversion of substisolved at low temperature and identified v i a the direct ‘5X-H coupling of 32.4 tuted cis-decalin has been studied (766, $9). I t is claimed that the phenanHz (537). Aromatic nitroso compounds threne skeleton is distorted only when are assigned predominantly quinonoid there are two “inside” methyls (443). structure if ring shifts show hindered High barriers to the propeller F! helix Ar-?; rotation (656). 4-Amino quinohelix + propeller equilibria are measlines are shown to have imino form in neutral media and amino form in basic ured for tri-o-thymotide (1578) and tri-o-carvacrotide media (1741). Aromatic character is (529). Inhibited pseudorotation is seen in a cyclic attributed to *-electronic interaction through the hydrogen bond of 2monoalkylphosphorane (810). Exbenzylamino - 4 - benzylimino - 2 - pentene change between two distorted octahe(521). Tautomerization of 1,3-cyclodral configurations is found for Snhexanedione was studied to obtain (acac)2Clz, with activation energy 5.4 equilibrium constants for keto F! enol kcal/mole (1091). A major review article on conformations of manyand enol F! enol processes (453). The membered rings gives some basic reftautomeric equilibria of a number of aldoses were studied in DzO (1244). erences to S M R work (455). Rotational Conformation. HinFast reversible valence isomerism is dered rotation is observed at lower studied profitably by KMR, as noted temperatures or by spectral variation in a review of the subject (1848). Kinetic studies reported include inverwith temperature for 1,2-dineopentyl tetramethyl benzene @ I S ) , 5,5-subsion of cyclooctatetraenes (862, 1586), stituents on 1,3-dioxanes ( 7 4 ) ; about a and alpha-methyl oxepin toluene 1C(0)-CH2 bond in ethyl trichlorooxide (848, 850). Complexes o f cyclooctatrienes with transition metal caracetyl acetonate (for which J,,, = 1.5 Hz) (488); about C(0)-OR (2235); bonyls also show slow ring inversion at &bout C(0)O-R (via ‘3C-O-C-H very low temperatures (1173, 437, 436, 1096, 1688, 68, 293). Valence taucoupling) (1077); S-S of diethoxytomerism is reported for u cyclodisulfide (2028); Ar--OC(O)R (1907); 820, 643, 2051, 541). Also reported are
582 R *
ANALYTICAL CHEMISTRY
pentadienyl metal complexes (729, 214s, 657). An allene-metal complex shows the metal-ligand bond alternating between the orthogonal a orbitals of the allene (activation energy of 9 kcal/niole) (168). Valence tautomerism is shown by NAIR for [24]annulene (519), for tricyclo [ 3 , 3 . 1 .O2 e ] nona-3,6-diene (183), and a novel sandwich compound [C7H7 ?J-C7H7] + (2188). Deuterium Labelling is a useful means of following the course and rate of a reaction. Usually, changes in the proton spectrum are examined. One of the methylene protons of benzyl methyl sulfoxide exchanges preferentially with water in YaOD-D20 (1723, 2177). Stereospecific deuterium migration is observed in reactions of norbornane derivatives (164, 165), and x-per deuteromethylation of certain azabicyclic systems gives preference to one of two possible orientations (975). Quaternization cif r-alkyo piperidines was shown to be preferentially axial by use of CeH&&and C6H5C&-alkyl groups (284). Methods of deuteration rate determination by proton S M R are discussed for ketones (937) and for aromatic proton exchange of phenols (141I). Erythro us. threo diastereomer distribution in X(C6H5)CH-cHDC6H5 may be determinable via the H-H coupling value (1119). ASSOCIATION PHENOMENA
Medium Effects. Solvent effects can be attributed t o combinations of association (H-bonding and the complexation), diamagnetic anisotropy of the solute (usually in combination with preferred orientation) , and electrical interactions. Generally, chemical shifts are affected more than spinspin couplings. These aspects have been reviewed ( d l 3 2 ) . ELECTRICAL EFFECTSusually are viewed in terms of a reaction field between polar solute and the solvent, and Van der Waals forces. Although the behavior of chemical shifts supports electrical interactions by general correlation with solvent dielectric constant or polarizability (148, 1165, 992, 1419, 886, 1950, 578) existing theory is not adequate, as demonstrated by solvent effects for ketones as vapor and in solution (677). Results for polar gases agree well with nuckingham’s theory while nonpolar gases in solution did not show the estimated Van der Waals contribution to shift (465, 2150, 6151, 466). Direct and indirect couplings among various nuclei show varying degrees of dependence (and nondependence) on various electrical characteristics of the solvent (990, 991, 433, 40, 506, 2114, 2117, 980, 441). Some theoretical gains have been made. X refined theory for nonpolar gases incorporates Van der Waals in-
teractions and averaged intermolecular distances (1803). A semiempirical approach to the effects of polar and nonpolar solvents on chemical shifts is presented (1470, 1471). Calculation of rotational equilibria in substituted ethanes as a function of solvent character is based on energy differences due to electrical effects (10, 9, 8). This approach has been used to calculate Jpouclc and Jc,,, values in the course of estimating the equilibria. AROMATIC SOLVENTS often cause significant distinctive shifts, which are used a great deal to characterize molecular geometry. These shifts are temperature dependent and attributed to aromatic ring current effects on preferential orientation between solute and solvent. Such observations lead naturally to the concept of complex formation via the r-electron system of the solvent. AH values of ca. - 1kcal/mole have been obtained for such complex formation (usually assumed to be 1:1)-systems studied include ketones and benzaldehyde in toluene (1132, 1214, 1131); DMF in various aromatic solvents (1819); and methoxybenzenes in benzene and toluene (253). blixtures of polar aromatic compounds and benzene were treated as weak n complexes in some nonaromatic solvents (1528). Self-association of tricyclic aromatic aldehydes in CDC13 solution has been characterized (854). A study of toluene relaxation and enhancement by dynamic polarization via dissolved free radicals interpreted the results in terms of electron-proton dipole-dipole interactions, obtaining activation energies for translational and rotational motions of the complex (1176). Such association has been considered t o arise from dipole-induced dipole interaction with the ring, such that the negative end of the solute dipole is directed away from the aromatic ring (290, 1783, 1784). It should be noted, however, that specific complex formation may not be required to explain these effects-shifts of comparable magnitude and their temperature dependence are calculated for benzene solutions by assuming complete randomness in the liquid state (1849. Many studies of aromatic solvent effects on protons in various structures have related their shift changes from nonaromatic solvent values to particular orientations and to placement in the solute molecule. Effects of various aromatic solvents are reported for acetonitrile (as well as many simple compounds in cC14 and in benzene) (1225) ; alicyclic ketones (419); and aluminum P-diketonates (1269). Shift differences between cC14 and CDC13 and benzene solutions are reported and discussed for various 1,a-dioxanes (48); a variety of ketones (2030, 2158, 2160, 740, 252); lactones, lactams, and acid
anhydrides (418, 1872, 1533, 1476) ; three-membered rings (1875, 1874,255); substituted dimethyl anilines (1696); aromatic methoxyls (621, 254) ; methoxyls of dimethyl phosphonates (162). Toluene as solvent was studied for oc,p-unsaturated ketones (1782). Solvent effects of pyridine have been studied for steroids (880); ketones (2157); and tropolones (1001). The olefinic protons of benzalmalononitriles exhibit large upfield shifts in benzene, and large downfield shifts in acetone (2125).
OTHERSOLVEKT SYSTEMS and effects have been reported. Liquid ammonia is proposed as a solvent for the study of weak acids (187, 189). Arsenic trichloride and arsenic antimony chlorides dissolve phenolic and polyimide polymers (1990). 1Zolten sulfur can be used (997). Tetranitromethanes can be used to modify aromatic anisotropy effects by n-complex formation (310). Proton spectra are surveyed for a large number of aliphatic compounds in CCb, trifluoroacetic acid, and trifluoroacetic acid-sulfuric acid (1625). Many thiazoles were observed in fifteen different solvents (2098). Water. S t u d y of structure of water and aqueous solutions b y NMR continues to receive a great deal of a t tention. Although most work uses OH resonance, where changes in shift reflect changes in H-bonding, much valuable information can be gained by examining l7O, as well as the nuclei of dissolved species. Various models for liquid water have been proposed and reviewed, with consideration of YRIR results (1498, 1583, 2148, 1811). Most K M R studies are concerned with evaluation of the extent of hydrogen bonding as a function of temperature and bolute. Careful measurement of proton shifts have been made for the liquid over its temperature range and for the gas a t various pressures in one study (936). An upper limit is given for the mole fraction of nonhydrogen-bonded OH groups in liquid water (898). Another discussion of NMR results includes new data on aqueous solutions of alcohols and carboxylic acids (1806). Careful measurement of proton T1 between 2.1' C and 95.2' C showed that spin-rotation is important near 100' C (1179). Measurement of T1 and T zas a function of temperature, pH, (2-12), and magnetic field shows that T1 is independent of p H and frequency but T z is dependent on both pH and frequency; proton exchange rates were measured (794, 795). Proton T I was studied from melting point to critical point temperatures for water in DzO and for ammonia in XD3 (1923). The macroviscosity of aqueous solutions of glycogen does not affect the water correlation time, as shown by T1 measurements (1697). Proton relaxation has
been studied for water containing molecular oxygen (0.01 to 200 atm) as a function of temperature (20-300' C) and frequency (907). hlolecular oxygen in alcohols enhances proton exchange and reduces the activation energy; the heat of solution can be obtained by this method (742). Deuterium T1 for D,O containing 15% HzO, studied from 0' to critical point, indicates strong hydrogen bonding even a t high temperatures (1666). Theoretical calculations of deuteron quadrupole coupling in free and hydrogen-bonded DzO lead to the conclusion that the major effect of H-bond formation is a lengthening of the 0-D bond (2129). Water 1 7 0 shifts are reported as a function of temperature in free water, and as a function of electrolyte content and dilution in several organic solvents. I t is concluded that 1 7 0 shifts 16 ppm upon breaking a hydrogen bond, and that the main cause of shifts in electrolyte solutions is interaction with ions rather than change of the structure of water (1315). At -12' C , the proton spectrum of ice is relatively narrow, and shifted f2.2 ppm from steam; it is concluded that the hydrogen bonding in ice differs from that in liquid water
+
(22)*
Aqueous Solutions. Aqueous electrolytes have been investigated in terms of hydration and kinetics of hydration by various means. Hydration numbers can be obtained when a separate absorption is observable due to the hydrated species. I n water solution this is found only for some paramagnetic ions, when contact shift occurs. Such was the case for l7O of water complexes mith the paramagnetic ions gallium(II1) (647) and vanadyl (IV) (1754). In the vanadyl case a second kind of fast-exchanging hydrated species h a s detected. An empirical equation has been proposed using proton Tzvalues when manganous ions are present to obtain hydration numbers for other cations (1980, 1437, 1981). Another approach compares temperature dependence of proton shifts with free water values to obtain a primary hydration number for the dissolved salt (1374). In a study of proton shifts in aqueous solutions of several paramagnetic ions it was found that there are five water molecules in the first hydration sphere of CO+2 bound t o RNA or inorganic phosphates (therefore, Co bonds t o only one site in RK.1) (1512). Sodium metatungstate in water displays a separate proton peak attributed to the two protons in the central tetrahedral cavity of [H2W12040]-6 (1650). I t is observed that the isotropic proton shift for water in the primary coordination sphere of Co(I1) is affected by presence of other ligands; this complicates the use of bulk solvent shifts to determine the number displaced by VOL. 40, NO. 5, APRIL 1968
583 R
another ligand (973). Characteristic ionic shifts are reported for protons of saline solutions (582). Kinetic studies were made of water exchange from the first hydration sphere of paramagnetic ions, utilizing proton resonance for V+2 (1983), Xi and Cr (1982); I7O for V f 2 (2187), Gd(II1) (1389), and Cu(I1) (1259, 1260); 1 7 0 and 14N for Ni(I1)-thiocyanate complexes (1061); and l7O and W I - with Fe(II1) (2222). Substantial relaxation of F- and PF6- occurs in the second coordination sphere of paramagnetic ions having nonlabile inner coordination sphere (1964). Most of the above studies and another (2121) also consider the mechanisms by which the contact shift occurs. The application of proton TI measurements to hydration studies is reviewed (928). Earlier work on T1 in ionic solutions is criticized (617). Attempts have been made to evaluate the effect of solute on solvent structure itself, as opposed to solvent-solute interactions (695, 793). It is noted that internal chemical shift references are not satisfactory (695). Quadrupolar relaxation of solute ions reflects environmental symmetry (thus, hydration and ion-ion interactions) and motions of the complexes (490, 2219, 2074). Chemical shifts and relaxation times have been studied for 'Li salts in various solvents including water (24, 1336); cations of alkali metal halides with consideration of anion effects (491); 133Csas affected by anions and paramagnetic cations (1310); 23Na(574, 575); and 1151n (327). A1Cl3 in mixed amide-water solvents gives separate organic complex absorptions (704, 940). Halide salts in methanol affect OH shifts in a manner similar to effects on water (903). MICELLARSOLUTIOSShave been studied by proton T1 of surfactant and solvent H O D (I%?,$), observation of W r - counterions (Gob), and I 9 F of perfluoro soaps (1500). In these and other cases, abrupt changes are seen in some shifts upon passing critical micelle concentration, including observation of second phase (605, 1010, 719, 1562). d review cf theoretical and experimental studies of surface phase systems emphasizes 1JMR results (603). Complexes in Nonaqueous Solution. Solvation of metal ions has received a great deal of attention. Observation of separate absorptions for solvated species allows determination of ion solvation number and exchange kinetics. Co(I1) and Ni(I1) cause dramatic effects because contact shifts are large; their solvation has been studied via proton NJ1R in dimethyl sulfoxide, dimethyl formamide and acetonitrile (1428, 1211, 2025, l 7 2 4 ) , and in D M F via 170NAIR (122). D M F solvation of other metal ions, especially AI(III), has been studied by proton
584 R
ANALYTICAL CHEMISTRY
ShIR (707',706,706) and by n A1 NMR (1486). Aluminum-solvent
complexes are seen separately also in DMSO (2024) and in liquid ammonia (788). Solvation numbers for all above cases have been measured as six. Mg+* (1625) and Np(V) (1883) solvation by methanol have been studied, the magnesium complex (solvation number 6) is seen separately at low temperatures. Electrolytes in liquid ammonia have been studied (787, 1979, 38, 2122). Selective ion solvation can be observed in mixed solvents (696,1846). Sites of metal ion binding in molecules are obtained from broadening of specific XMR lines. A function based on proton line widths is given to relate proximity of Cu(I1) ions to them in carboxylate shifts and splitligands (510). The tings of phosphate polyanions reflect specific site binding of metal ions (445). Temperature jump relaxation times for adenosine triphosphates complexes with various metal ions agree well with published S M R correlation times (878). The shape of dimethyl- and diethylthallium (111) was found to be sensitive to solvents, and the TI-H coupling varied with donor strengths of the solvent for linear cases (1885). The adduct BF,. H20is seen a t low temperacoupling tures with observable H-F (783). Proton, I9F and IIB data are reported for a large number of boron complexes (925). Relative donor or acceptor strengths may be obtained simultaneously using chemical shifts and series of acceptors (or donors) with a common donor (or acceptor) (690). It was found that displacement of donor chemical shifts on complexation with pallium is not a good criterion of stability (832). However, 1lB shifts of boron trihalides complexes are reported to reflect complex strength (763). The fluorine shifts of p-fluorobenzophenones are useful for predicting their enthalpies of reaction for formation of Lewis acid adducts (774). Aromatic fluorine shifts of perfluoroaromatic electron acceptors were used to obtain equilibrium constants of charge transfer complexes with methyl benzenes (285). Association constants of aromatic charge transfer complexes are obtained from chemical shift variation with concentration of donor species (688). Hydrogen Bonding has been studied in a variety of systems. Kinetic studies have been made of water association with DSIF, acetone, THF (1993), and dioxane (1503). Monomer-polymer equilibria are reported for various substituted phenols (837). Phenol-base complexes show correlation of OH shift with AH for H-bonding (616A) and with pK, values for the bases (1941). Hydrogen bond shifts have been estimated for diols as the difference between OH shift at the melting point and calculated free OH shift (22209). A method is
given for obtaining dissociation constants of methyl alkylketone cyanohydrins (1873). The use of rigorously dried solvents for carboxylic acids has permitted reliable extrapolation to infinite dilution (1602, 1601). IaC=O shifts for acetic acid in various solvents were examined with concentration, reflecting H-bond changes (1558). CHC13 shifts in a large number of solvents are found to be characteristic of functional groups in the solvent, correlating with atomic orbital dipole moments to indicate a measure of hydrogen bonding strength (725). In sterically hindered alkyl amines the CHCls proton shift is attributed to an association equilibrium and correlates linearly with Taft's E, parameters for alkyl groups (724). Anomalies in CHCI, shifts due to steric effects also are noted in determining basicity of certain organometallic bases by chloroform dilution shift ( 2 ) . It is suggested that the (O2N-0-H-O--NO2) - ion may contain a symmetrical hydrogen bond (620). Broad-line S J I R results are the basis for suggesting nonlinear hydrogen bonds in CaSn(OH)6 and ZnSn(OH), (405). Careful studies of alcohol association are noted (631, 1678, 180). Inter- and intra-molecular hydrogen bonding has been evaluated for salicylaldehyde (1565). Dissociation of perchloric acid was studied by both proton and asC1 NMR (23) Monomer-dimer equilibria in amines have been investigated (46, 1413, 1412). Diethylamine hydrogen-bonds more strongly to acetonitrile than to itself. (1953). Acetamide-amine association has been studied (1992). Chloroformnitrogen base complexes have been characterized (170, 664). Hydiogenbonding is studied in thiols (1791, 1792, 1387) and in thiocarboxaiiiides (538) p H dependence of C-H proton chemical shifts and coupling constants for carboxylic acids has been studied, as well as OH shifts Chemical shifts of alpha protons change significantly. Vicinal coupling constants generally vary relatively little, implying that p H has little effect on rotational isomers. Evidence is found for intramolecular H-bond formation in some dicarboxylic acids a t half-neutralization (1284, 1912, 81I , 1594). The amino acid, serine, shows large temperature dependence for the cation, but not for the zwitteiion or anion (1568). Protonation by strong acids can be characterized conveniently by SJIR. Applications t o general amine structure determination are described (68, 716A). The basicities of phosphine oxides and phosphine sulfides can be determined from PCHI proton shifts as a function of H2SO4 concentration (863). Rate constants for the protonation of some e-p-unsaturated-p-aminocarbonyl compounds occur in the sequence KO>> I
I
IiN>>Iiru-c (1168). Protonation of methoxybenzenes may occur a t the oxygen as well as a t the carbon (281); and C-protonation causes slowing down of these methoxyl group rotations a t -83' C (282). Cyclooctatetraene is shown to protonate preferentially on the "inside" of the ring, with subsequent ring inversion ( 1095, 217 3 ) . Protonation of the carbonyl oxygen of ketones, aldyhydes, and carboxylic acids is shown to give both syn and anti isomers in many cases (953, 954, 277). Protonation of p-diketones is found to give both mono and/or dication structures, with slow exchange between them when both are present (280). Protonation of p-nitroso-x,x-dimethylaniline occurs a t the oxygen, causing slow rotation about the ring-X bond and imparting quinoid character to the ring (1369). Dynamic Polarization of nuclear spins can be achieved by thermal mixing at low magnetic fields with spins having quadrupolar properties, followed by adiabatic magnetization (797). Enhancement o f solvent nuclear signals upon irradiating electron spins of dissolved 2,4,6-tri-t-butyl phenoxy radical was observed, leading to evaluation of diffusion kinetics (555). Protons of liquid deuterated hydrogen have been polarized dynamically by paramagnetic coals (12%). OTHER TOPICS
Nuclear Spins and Moments. Two precise measurements of the proton g factor were reported. B highly accurate free space value, gP
=
0.0030420652 (9) = 2 p p / p
where p is the Bohr magneton, was obtained from observation of atomic hydrogen via a hydrogen 1IAZAR experiment (1517). An experiment observing water proton frequency and cyclotron frequency using the omegatron method gave p,(H,O)
=
2.79274 (5) n.m. (1627).
The gyromagnetic ratios of 'H, 3H, and free electron were measured in terms of the electronic gyromagnetic ratio for *5Rb, v i a spin exchange optical pumping, to an accuracy of 5 parts in 108 (116). Spin and/or magnetic moment values were reported for the following nuclei: 17F(I= 5 / * , I.( = 4.7223 (12) nm corrected) (1984); 24?;a (1.69025 ( 5 ) nm corrected) (357);37.-lr ( 3 / 2 , 0.95 (20) nm) (1775); 43Sc ($7.61 (4) nm uncorrected, Q = -0.26 =k .06 b) and 47Sc (+5.33 (2) nm uncorrected, Q = - 0.22 (3) b) (433); 45Ti (7/z, 0.095 ( 2 ) nm uncorrected, Q = 0.015 (15) b) (434); 57Fe (+0.09024 (7) nm) (1281); 110~~~Ag (+3.587 (4) nm uncorrected) (1837); la5Ba (0.83651 (6) nni corrected) and 137B (0.93573 (6) nm corrected) (1579); I4?Pm (+ 2.58 (7) nni, Q =
+
+
0.74 (20) b) (1731);lS1Eu(3.4630 (6) nm) and 15)Eu (1.5292 (8) nm) (613); 1'37Er(- 0.5647 (24) nm) and 14SNd (- 1.063 (5) nm) and 145Nd (- 0.654 (4) nm) (1926); "j9Tm (0.2310 (15) nm corrected) (779); I87Os (0.06432 ( 3 ) nm corrected) (1089); 14%rn and lr9Sm (2181). The following resonant frequency ratios were reported: 199Hg (vapor): lH = 0.1782706 (3); l"Cd (vapor): IH = 0.2117828 (5); and 113Cd (vapor) : 1H = 0.2215426 (1227). A comparison of the resonant frequencies of 'H with those of SH, 'Li, 11B, and 19F, all in the same sample, showed no field dependence within 1 part in lo7 going from 23.5 gauss to 10.8 kilogauss. The authors conclude that a field dependence for yp is unlikely, but not ruled out entirely (985). Organometallic Compounds. General proton X M R studies have been reported for tetraalkyl ions of Group 111 and V atonis (377~4,1716), alkyl complexes of Group V and VI elements (731); gem-diamine complexes of Group IV (1717) and acetylenic derivatives of P, Si, Sn, and Pb (1913) solution (188, 1881). PH,, AsH3, SbHa, and SeH3 are observed (568). Fluorophosphine ligands on zerovalent nickel and molybdenum have been studied by 19For S M R (1734). Proton N M R data are given for trifluorophosphine complexes of transition metal hydrides in a review article (1175). 170, l*N, and 13C chemical shifts are reported and discussed for a series of transition metal complexes (262). Proton shifts of pdiketone complexes of Group I11 and IV elements are sensitive to electrical symmetry (1925). Methyl (1839) and alkyl (540) stannanes display decreased hydride proton shielding as substitution increases, attributed to Sn-C bond anisotropy. The germanes showed the same effect, correlation also being observed in the J H c X H values for both Sn and Ge (1839). In alkyl and phenyl stannanes Jlleg,-R correlates with the Sn-H stretching frequency, and both are related to U * functions (1364). Studies of tetra-alkylated tin coinpounds included consideration of dlr-pn bonding in tetravinyl tin and tetraallyl tin (202) and proton and fluorine spectra of some fluorinated organotin compounds (384). bIossbauer chemical shifts of tin and Jsn-c-H couplings are found to be related, as expected, since both depend on electron density a t the Sn nucleus (1115, 1432). Sources of proton shift and coupling changes have been investigated for the ethyltin chlorides (this article reviews theoretical aspects as well) (2089), various ethyltin compounds (2091), and inethyltin halides (2075). Jsn-cnaof trimethyl tin chloride adducts appears to be related linearly with their enthalpies of formation (223).
Germanium compounds behave in a fashion similar to tin. Spectra of a number of ethyl germanium compounds have been examined, with the conclusion that magnetic anisotropy of substituents on Ge dominate the ethyl proton shifts (1339). Hydride proton shifts have been studied for a number of organoand organohalogeno-germanes (1418, 1824). Application of NRIR to silicon hydride studies is reviewed briefly (566). In a study of Group V trisilyls, X(SiHJ8, an isotope effect of 29Si us. %Si on the proton shift was observed, and like signs (567). mere found forJs,-a and Js,--P-s~-H In a variety of mono-, di, and tri-substituted silanes incremental shielding by F, N, and 0 may be related to (p-d)n bonding (326). The same conclusion is reached in a comparison of methoxy and methylthio derivatives of C, Si, and Ge (449). Shielding of alkyl protons in some siloxanes is attributed only in part to inductive effects (961,1584). Platinum(I1) complexes have been studied via 31P shifts of complexed tertiary phosphines (839) and oia 19F shifts of meta- and para-fluorophenyl complexes (1602). In the latter case correlation is found between u donor characteristics, as measured in this fashion, and basicity of associated anions. Changes in J P ~ - c of-platinum -H (11)-ethylene complexes are attributed to change in Pt-C2H4bond length (1026) or s-character in the Pt-ligand sigma bond (264). Proton data are listed for a number of trimethyl platinum compounds (1126). Lithium exchange in the system Li+/ fluorenone- -LiBr appears as a teniperature-dependent 7Li line u idth, attributed t o dephasing of 7Li spins by quadrupolar interaction upon association nith the fluorenone (330). Hindered rotation or exchange is exhibited in the proton spectra of tricarbonyl (t-butyl- and isopropyl-benzene) chromium (817 ) and trisallylrhodium (149). Rapid cis-trans isomerism was studied via the bridge protons of some alkylberyllium hydrides (158). J207Pb-C-H correlates linearly with U* values of the alkyl group (1917 ) . Proton spectra of metallocenes reflect correlation of shifts with Taft and Hammet substituent parameters, as well as ring-current effects (146, 1495, 311, 1541). Substituent additivity ruleq are presented for ferrocenes (2094). It is concluded that there is no pseudocontact interaction in the ring proton shift of paramagnetic ferricinium cation (727, 728). Contact shifts are studied in a number of paramagnetic methyl substituted metallocenes, some results contradicting the usual r-delocalization model for such shifts (1750). 4 study of paramagnetic transition metal acetylacetonates concludes that isotropic shifts in first transition row VOL. 40, NO, 5 , APRIL 1968
0
585 R
compounds are dominated by contact interactions, while pseudo contact effects become important for second transition row compounds and dominate in rareearth compounds (563). I n contrast to this is the conclusion that pseudocontact shifts are of significant importance in high-spin tetragonally distorted hexacoordinate cobalt (11) complexes (1136). Spin delocalization in mixed tetrahedral Si(I1) complexes is correlated with Hammett sigma parameters (565). I n a study of spin density transfer in octahedral and five-coordinated Schiff base complexes with Ni(I1) it is concluded that the unpaired spin is effective in the ligand highest bonding and lowest anti-bonding n-orbitals (1192). Spin delocalization was studied in substituted anilines complexed with Xi(11) (1135), It is noted that analysis of high resolution spectra of metal complexes containing two or more phosphorous nuclei (which are coupled t o one another) should not ignore coupling between ligands, especially when symmetrical (890). Biological Applications. Broad coverage of this area is t o be found in “Proceedings of the Second International Conference on Magnetic Resonance in Biology” (1677) a n d a n article on “Rlagnetic Resonance in Pharmacological Research’’ (1026). A “halogen ion probe” technique has been demonstrated for observing sites of metal binding (specifically, Hg) in proteins (1962). Broadening of quadrupolar chloride ions occurs upon attachment to Hg, small or no effect being observed when first coordination sphere is not available. The method has been applied to observation of helix-coil transition ( 2 9 4 , reactivity of sulfhydrile groups of hemoglobin (1968), and antibodyhapten interactions (902). Phosphorous spectra were used to show that paramagnetic ions bind to the phosphate groups of ribonucleic acid and adenosine monophosphate (1896), and simultaneously t o all three phosphates and the adenine ring (by proton X l I R as well) in adenosine triphosphate (1967, 1968). Evidence from 15N N M R indicates that l I g + - 2does not interact n ith the adenine system of adenosine triphosphate, but Z n f 2 may (885) and C u + *interacts with the adenine ring of adenosine monophosphate (1908). The intermolecular complexing of penicillin with serum albumin was studied by N l I R relaxation, showing that the binding site is the phenyl ring (658). Evidence for base stacking and insertion is found in a proton XLIR study of purine bonding to dinucleotides, in D 2 0 (865). Hydrogen bonding is found between inosine and other nucleosides in CDC13 solution (1836). Methoxyl proton shifts were used to assign structures to quinones, chromenals, and chromanols of the coenzyme Q group
586 R
ANALYTICAL CHEMISTRY
(1473). Characteristic shifts of methyls attached to epoxide rings and splitting patterns are considered (143). An empirical analysis technique is proposed for identifying some ABCD and ABC patterns (623). Biosynthetic processes are studied by examining metabolites derived from W-enriched acetate (2008). Nonprotein moieties of biological membranes can be observed via high resolution spectra of suspensions or dispersions (359). General K l I R methods are reviewed for studying triterpenes (1381) and additivity rules given for methyl shifts (2064, 1831). Substituent effects are studied in diterpenes (80). The direction of enolization in a number of ptriketones was determined via shifts of adjacent gem-dimethyls (181). Cis us. trans fused decalins and steroids may be differentiated on the basis of breadth of angular methyl absorption (2165). XMR studies of a large number of similar structures are reported for steroidal cyclic thioketals (1895); spirostans and similar steroids (824); meliacins and derivatives (1661); and some gibberelin derivatives (884). The spectra of a large number of steroids in DMSO solution differ little from their spectra in CDC13 (829). Detailed spectral analyses of some alkaloids are made and interpreted fully (447). Large tabulations of alkaloid data are noted (448,1409). KJIR is quite useful for determination of amino acid sequence in di- and tri-peptides (1878). Characteristic shifts are found for alpha-CH protons of amino acids as cation, zwitterion, or anion (1524). a-amino acids can be distinguished from their 8- and yisomers by shielding of their carbomethoxyl protons upon tritylation of the amino function (1957). -1 detailed N M R study of methyl derivatives of cytosine has been made (152). Strong intramolecular hydrogen bonds are found by N I R in monocations of sparteine- and a-isosparteine-S-oxides (1178). S M R study has been made of helix-random coil interconversion in model polypeptides (1969, 1970). Methyl, olefinic, and functional group protons are considered for a large number of derivatives of vitamin d (1483, 1484). Complete NMR data are reported for many derivatives of isoglaucanol (764). A review of sugar-phenylosaxones includes detailed discussion of N M R results with suggestion of an openchain chelated structure (1446). Conformations of glucose and polyglucoses have been studied in D N S O solution (341, 342). Other studies have been reported of glucose polymer conformation (790); c-methyl-branched sugars and cyclanols (1264); amino sugars in D20 (1009); and acetylated amino sugars (97’4). Proton spectra can be
used to distinguish orientation of ribonucleoside derivatives (733). Absorbed and bound water has been characterized in biological material by broad-line proton NMR. Hydrated oriented D N A gives angular dependence of spectra similar to collagen, in disagreement with an earlier report (1805). Normal sciatic nerves of rabbits give an anisotropic curve, while degenerate nerve gave a singlet (1008). Water is hydrogen-bonded to albino hair (394). The proton line width of fillet of freshly killed cod decreases during rigor mortis, implying loss of bound water by cell protein (1977). Organic Ions. N M R spectroscopy has made available much significant information about organic ions. Two review articles cover the area of carbonium ions, which are studied most (1574, 371). Relative stabilities of carbonium ions may be obtained by mixing equimolar amounts of a stable carbonium ion salt with a precursor, so that the rapidly equilibrated mixture displays the two ions in amounts proportional to their stabilities (2216). Direct 13C-H coupling of 127.51 Hz at C 9of anthreconium ions was taken as evidence for sp3hybridization (1156). Polymers. One review of applications of high resolution, broad-line, and pulse techniques contains m a n y spectra, including protons at 200 MHx (31). Another review of the three approaches also discusses present status and future problems (1548). Experimental procedures of these approaches are discussed for study of poly (vinyl chloride) (2009). A rather thorough review discusses the study of tacticity and conformations of several vinyl polymers via high resolution N N R and I R studies of the polymers and model compounds (1886). In similar reviews of K J I R work it is indicated that the X M R gives only limited, but valuable, conformation information (248, 249). NMR, IR, GC and mass spectrometry are compared for determination of molecular weight and molecular weight distribution in rubber and rubber products (2065).
Steady state and transient NMR techniques are compared with dynamic mechanical methods for the study of segmental motion of high polymers (2184). hIultiple relaxation processes observed in a series of polyolefins, poly(alky1 methacrylates), natural rubber, polyisobutylene, and polybutadiene are correlated with dynamic mechanical and dielectric relaxation results (1920). HIGH RESOLUTION.Ordering of chemical shifts due t o tactic structures is discussed in terms of bond anisotropy, Ivith agreement found between the observed a n d calculated shifts of t h e methylene protons of isotactic polypropylene (1770). It is noted that the
shift for a syndiotactic unit in a chain that is mainly isotactic should not be the same as for such a unit in a syndiotactic chain (664). The resolution of tactic effects is very dependent on solvent, as demonstrated for poly(methy1 methacrylate) (PMMA), poly(viny1 acetate) (PVA), and poly (a-methylstyrene) (1708). Arsenic trichloride and arsenic/antimony chlorides are useful solvents for phenolic and polyimide polymers (1990). Emphasis has been placed on analysis of spectra of homopolymers, often with the aid of smaller model compounds. Meso- and racemic 2,4,6,8-tetramethyl nonane were synthesized to serve as model compounds for isotactic and syndiotactic polypropylene respectively; indeed, their N M R and I R spectra bear strong similarity t o the corresponding polymers (1639). On comparing the observed methylene proton spectra of syndiotactic polypropylene (60 or 100 MHz a t 170’ C in C&X) with spectra calculated for nine rotational conformers, using appropriate coupling constants, it is concluded that there is rapid conversion among the conformers (1569). The spectra of highly iso- and syndiotactic polypropylene in orthodichlorobenzene a t elevated temperatures are discussed (228). On the basis of these differences, and assignment of methyl absorptions for iso-, hetero-, and syndiotactic triads it should be possible to determine tacticity (2180). I n another report polypropylene tacticity determinations of the spectra were run in diphenyl ether a t 200’ C (1656). Stereoisomers of 2,4,6-triphenyl heptane, a model compound for polystyrene, were prepared and separated, and then N M R spectra were analyzed (1265). Significant changes in the linewidth of the phenyl peaks of isotactic polystyrene, up to 100’ C, are correlated with local mobilities in the chain (1738). N M R was used to characterize polymers of 3-methyl-I-butene ( 9 8 4 , 3-chloro-3-methyl-1-butene (1099), 4methyl-1-hexene (1100), cyclopentene, 3-methylcyclo-pentene, and 3-methylcyclohexene (229), and oligomer of isopropylcyclopropane (1518). hlolecular motions were studied for low-molecularweight isotactic polystyrene in solution via linewidths, second moments, and TIT2 products between 0 and 95’ C ; the previously reported transition a t 40’ C was estimated a t 2 kcal/mole from the TlT2 data (2127). The preparation of model compounds of vinyl polymers has received much attention. A thorough set of spectra was calculated for various conformations of vinyl polymers and applied to the stereoisomers of 2,4-pentanediol and 2,4,6-heptanediol and their acetates, as models for poly(viny1 alcohol and acetate) (743, 741). The spectra of mesoand racemic 2,4,6,8-tetramethyl nonane
polypropylene bear strong resemblance to isotactic and syndiotactic polypropylene, respectively (1639). Isotactic, heterotactic, and syndiotactic 2,4,6tricarbomethoxyheptane (poly(methy1acrylate) (1266, 387) were converted to the corresponding acids (387). The stereoisomers of heptene-2,4,6-triacetate (poly(viny1 acetate)) indicate that the acetoxy shielding increases in the triad order isotactic-heterotactic-syndiotactic (737). Spectra are given for the three stereoisomers of 2,4,6-tricyanoheptane (1505), and those of meso- and dl-2,4 dicyanopentane were used to assign tacticity to poly(acrylonitri1e) and poly(a-deutero acrylonitrile) (1423). The stereoisomers of 2,4,&trichloroheptane (poly(viny1 chloride)) were reported (522) and their spectra a t 60 and 100 RIHz analyzed completely via use of spin decoupling (1, 1888). Computer calculations of poly(viny1 chloride) spectra are reported (1887)). cis- and trans - 2,5 - dimethoxy - 2,5 - dihydrofuran were analyzed as models for the cyclopolymer of succinaldehyde (19). In poly(methy1 methacrylate), PhZXA, of mixed tacticity the methylene “singlet” of a syndiotactic diad is resolved into three lines (due to more distant monomer units) (247) assigned to tetrad sequences (901). Karrowing of the a-methyl line in a syndiotactic sequence of PMMA occurs a t a higher temperature than for the isotactic sequence, which correlates with the glass transitions for is0 and syndiotactic polymers (1083); comparison of the widths of the a-methyl and methoxy lines with temperature permitted certain conclusions regarding conformation (292). Similar polymers reported were highly syndiotactic poly(@-phenylethyl (2201), poly (n-alkyl methacrylate) methacrylates) (1082), and poly(ally1 methacrylate) (2164). Poly(isopropy1 acrylate-@-dl) (2214), as well as poly(methy1 acrylate-p-dJ (2212) were examined for vicinal coupling constants; comparison with the couplings in trimethyl cis-hexahydrotrimesate lead to the conclusion that trans placement of the chains leading from a given C-C group exists -50% of the time, and that both gauche forms are nearly equally populated (2212). The spectra of poly(methy1 acrylate) and dimethyl &,a’-dimethylglutarate have been analyzed (1425). A detailed study of poly(viny1 acetate), PVAC, via the polymer and derivatives thereof (1705) concludes that the acetate methyl shifts have increased shielding in the triad order i, h, s, and that the a-proton spectra are not sensitive to backbone configuration while the @-protonsare. This methyl assignment reverses an earlier conclusion (1703) and agrees with others (1506, 737). Tacticity information was acquired also for poly(viny1 trifluoroacetate) via F(19)
spectra (1676), poly(viny1 formate) (1706), poly(viny1 formal) (738), and poly(ethy1-, isopropyl-, and tert-butyl vinyl ether) (1704). Tacticity of poly (acrylonitrile), PAN, has been measured on the basis of separate methylene triplets (2191), while more complete analysis with decoupling resolves the a-hydrogen triads as well (128). A study with a-deutero PAN gave similar resolution of structure but no quantitative results (2190). It has been shown that PAN tacticity cannot be measured by conversion to poly (methyl acrylate) because racemization occurs during hydrolysis (1424, 1758). This should not affect similar conversion reported for poly(methacrylonitri1e) (1422), for which conversion may not be necessary (1865). With decoupling of the a-protons of poly(viny1 chloride) , the more shielded methylene was seen as a doublet and assigned to tetrad shifts (1102). Another study of a-deutero material (250) matched observed spectra by adjusting proportions of tetrads observed in work on a, @-dz (8213). Previous postulated assignments of absorptions in poly(viny1idene fluoride) to head-to-head structures, etc., have been substantiated, as well as similar behavior in poly(viny1 fluoride) (2170). N M R is used extensively to characterize polybutadienes and polyisoprenes for cis- and trans-1,4; 1,2; and cyclic content, often by use of enhancing techniques (92, 545, 800,801,93, 366, 1872). Other diolefin polymers studied include several different polymers (185);cyclopentadiene (459); lJ2-polyallene (1687); 1,a-pentadienes (725); perfluoro-1,4pentadiene (6g9); and divinyl ether (91). N M R was used to characterize polymers of the following materials : itaconic acid (267), 2-substituted oxazolines (1070), benzoylenebenzimidazoles (415), L-lactide (1851), and propenyldiphenylphosphine oxide isomers (2130). Polyethylenes can be analyzed for methyl and olefinic hydrogen content by extensive enhancement (1084). End groups of low-weight ( D P < 200) poly(viny1 chloride) were determined quantitatively by KhlR (861). A thorough review of copolymer analysis by high resolution NhlR and relation to copolymerization equations treats MMA-styrene, vinylidene fluoridehexafluoropropylene, and vinylidene chloride (VDC)-vinyl chloride (VC) copolymers in detail (1045). A similar review also treats lJ3-dioxo1ane-styrene and 1,l-diphenylethylene-1lAlA copolymers (2196), while another review of sequence studies in copolymers covers a variety of physical properties including N M R (899). Although structure of the methylene proton absorption in VC-VDC eopolymers continued to be interpreted in terms of nonhead-to-tail sequences plus long-range effects (1326), (head-to-head VOL 40, NO. 5 , APRIL 1968
587 R
and tail-to-tail sequencing is surprising because it is not observed in the homopolymers) another report (1046) presented a very reasonable argument for the spectral features in terms of diads with further breakdown to tetrads and hexads, based on head-to-tail polymerization only. I n a similar fashion lines in VDC-isobutylene copolyniers may be assigned to diads, triads, tetrads, pentads, and hexads (926), while diads, and possibly tetrads were reported elsewhere (659). hIethoxyl lines of styrene-methyl acrylate copolymer were assigned in the same manner as for styrene-MMA (1616). The three methoxyl lines of a 1,l-diphenylethylene-methyl acrylate copolymer were assigned to have shielding increase with number of adjacent diphenylethylene units (1017). The various kinds of triads formed in the copolymerization of propylene oxide with maleic anhydride can be resolved by examination of lines from both kinds of monomer units (1107). QUANTITATIVE COPOLYMER AKALYSES by NhfR are straight-forward when separate absorptions are seen for one or both (or more) of the various units present. Of the many analyses of this sort reported, only one is mentioned here-a careful study of styrene-acrylonitrile copolymer (2006). Special care or techniques must be used !Then complete resolution is not possible. Such cases reported are ethylene-propylene block copolymers (1655, 1657) and very low level 1,4-isoprene units in conimercia1 grade butyl rubber (368). Among the many other studies of copolymer structures by NMR were propylene-styrene (1143), effect on PVC structure of the presence of 3-11% vinyl acetate as copolymer (soor), styrene-aromatic methacrylates (1015), acrylonitrile-M;\IA (1686), graft copolymers of paraisopropyl styrene and ethyl methacrylate (957), graft copolymers of phenolic novolacs on polyamide (1725),a-methyl styrene-p-meth11-a-methyl styrene (I17), butadienearomatic hydrocarbon telomers (1183), styrene-polysulfone (1000), polyesters of dithiols with diallyl maleate (1585)) homologous series of polymers of nylon 6, Kylon 66, and poly(ethy1ene terephthalate) (923), and acetylated styrene-cellulose graft copolymer (752). BROAD-LINEA N D PULSEDNMR studies of polymers furnish information regarding molecular motion via second moments and relaxation times. Some general discussions were given (2052, 2185, 379, 1019). A theory is proposed for relaxation of chain polymers in solution, based on Brownian motion of isolated polymer molecules (2067), then extended to the effect of side-chain motion (2068). Self-diffusion coefficients were obtained for polyisobutylene in benzene by the pulsed-gradient, spin588 R
ANALYTICAL CHEMISTRY
echo method (240). Very high pressure affects the structure of polyethylene and Teflon (392). A t 1.5' K methyl group reorientation persists, v i a tunnelling, in poly(methy1-a-chloroacrylate) (1142). Xo change in group reorientation at frequencies above lo4 sec-1 occurs between 77' K and 4.2' K for poly(tetrafluoroethylene), polystyrene, or PMMA (653). I n a thorough study of the role of inter- and specific intra-molecular motions in solid n-alkanes, T I minima were found a t 150 f 5' K a t 50 RIHz. It was concluded that at this temperature the methylene protons are essentially immobile, and that their spin-lattice relaxation occurs via spin-diffusion to the methyl protons. A kinetic model is developed which accounts for the dependence of the minimum T1value on the CH3/CH2 ratio (54). In this, and in a further study via pulse measurements of T1, (in the rotating frame) (527), an activation energy of 2.6 kcal/ mole is obtained for the methyl rotation. An analogous study of TI for poly(viny1 alkylates) also attributed low-temperature relaxation processes to terminal methyl groups (1451). The n-alkanes here are models for polyethylene. A broad-line study was made on polyethylene as single crystal and modified in various ways (1577). One study of poly(tetrafluoroethy1ene) examined relaxation processes by NMR, dielectric, and mechanical measurements (1732), while another NMR study included TI, (rotating frame) measurements (1322). Syndiotactic polypropylene was compared with isotactic and atactic materials in a broad-line study (373). Other hydrocarbon polymers studied include polybutenes (1153) and polyacetylene (1882),linear aromatic chains and aromatic polyesters (1426). Some polymers reported containing other nuclei than carbon in their chains were poly (ethylene glycol) and polyoxymethylene (933), polymethylsiloxamer (1228), and linear dimethylpolysilazane (1458). d comparison of polysilazanes with polysiloxanes showed no appreciable difference in flexibility of the backbone (118). A method is given for better measurement of both the rigid (broad line) and low-level mobile (narrow, easily saturated line) components of a spectrum and applied to Nylon 66 (1353). Oriented polymers studied included Nylon 66 (1354, 1365, 1356), poly(viny1idene (1206), poly(acrylonitri1e) fluoride) (1357, 1149), polyethylene (1624, 1576), hydrated poly(viny1 alcohol) (853), and a variety of elastically deformed oriented polymers (573). Analytical Studies. Practical aspects of applying N M R techniques t o chemical analysis are dealt with in books (360, 1417), chapters of books
(265,2131), and review articles or collections of papers (2005, 1400, 1561, 1973, 16.45, 1599). Applications to food analysis are reviewed (1147). Classification of chemical shifts by magnitude and by functional groups is discussed with respect to ease of searching for unknowns (2193). QUASTITATIVEhIEASUREMENTS by NMR are affected by electrical loss in the sample; thus, an increase in ionic strength of an observed solution is accompanied by decreased signal intensity per nucleus (1822). Another study of reliability of quantitative standards considered many other factors (1826). Good accuracy is attained by measuring low-level organic compound content by comparison of its integral with that of the satellites of the solvent acetic acid (3%). Techniques of isotopic analysis, particularly deuterium, by YAIR are discussed (2092, 1220). A clever method for detection of DzO in ds-DMSO involves observation of H-C-OH splitting for dissolved benzyl alcohol (1258). Deuterium content in D20-Hz0 mixtures is determined by observing relative amounts of deuterated and protonated benzyl dimethyl ammonium ion present (1263). Hydration numbers of solids can be obtained from measurement of total hydrogen when dissolved in D20 ( I 182). The 13C content of liquefied methane was measured at 3.8 =t 0.2% by comparison of '*CH : W H proton peaks (570). Quantitative measurement of 13C distribution a t natural abundance has permitted estimation of aromaticity in coal tar and oils (721). Fluoride content in solid A1F3 salts has been obtained by measuring peak-to-peak height of the fluorine broad-line derivative spectrum (640). ALCOHOLS can be characterized as l o , 2', and 3" on the basis of the fluorine shifts of their trifluoroacetate esters (1877, 1379). Another technique for alcohol characterization is to observe the -0-CHproton shift before and after methylation (1530, 1531). Observation of HCOH splitting in DMSO solution is not fully reliable in that OH exchange cannot be stopped always (2055). Components in mixtures of phenols can be analyzed by their OH peak positions in properly prepared hexamethylphosphoramide, where the shifts are down field from the aromatic proton region (502). Thiols may be identified more readily, or their spectra simplified, by in situ treatment with reactive isocyanates (309). DETERMINATION of hydrocarbon olefins by high resolution KMR is discussed thoroughly (1969). A method is given for determining olefinic impurities in alpha-olefins (661). Individual alkyl naphthalenes for which standards are
not available can be identified according t o methods developed from observations of others (2198). Polyurethanes give good spectra in AsC13 solution at looo C (260). Dialkyl polysulfides can be analyzed for mole-average sulfur rank by alpha-proton shift (1395). Mixtures of phosphorous and pyrophosphorous acids can be determined by their proton chemical shifts (198). Methods are given for analysis of some soporific drugs (1798,1799). Other interesting applications of NMR have been reported. Displacement of proton-containing liquids from porous sandstone by aprotic liquids, such as D20 or CCl,, has been observed b y monitoring the broad-line proton signal-e.g., DzO, CC14-(20S3). Crystallization of a supersaturated polymer solution has been measured by monitoring the liquid phase absorption (1236). The nature of plasticizing in polymers can be characterized by plasticizer TZ value (370). LITERATURE CITED
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0
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