Abstract
A new method for quantification of the relative distribution of deuterium in molecules is proposed. The technique is based on the lineshape analysis in the 2H NMR spectra obtained at the natural abundance level of deuterium with allowance for inhomogeneity of the magnetic field. The equilibrium thermodynamic H/D isotope effects for hindered rotation about the C—N bond in the N,N-dimethylformamide molecule and for prototropic exchange in the cyclopentadiene molecule were determined. The results obtained agree with those of DFT calculations of the vibrational energies.
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References
L. Melander and W. H. Saunders, Reaction Rates of Isotopic Molecules, Wiley, New York, 1980, 340 pp.
R. Hagemann, G. Nief, and E. Roth, Tellus, 1970, 22, 712.
M. L. Martin and G. J. Martin, NMR Basic Principl. Progr., 1990, 23, 3.
H. H. Mantsch, H. Saito, and I. C. P. Smith, Prog. Nucl. Magn. Reson. Spectrosc., 1977, 11, 211.
G. J. Martin, X. Y. Sun, C. Guillou, and M. L. Martin, Tetrahedron, 1985, 41, 3285.
M. A. Cremonini, D. Tacconi, V. Clementi, and C. Luchinat, J. Agric. Food Chem., 1998, 46, 3943.
T. Nakayama and Y. Fujlwara, Anal. Chem., 1982, 4, 25.
Xwin_nmr Software Manual. Part 1: General Features and Data Processing, Bruker Analitik GmbH, 1997, 185.
G. J. Martin and N. Naulet, Fresenius´ Z. Anal. Chem., 1988, 332, 648.
K. Ebert and H. Ederer, Computeranwendungen in der Chemie, Verlagsgesellschaft mbH, Weinheim, 1985, 370 pp.
U. Siehl, Adv. Phys. Org. Chem., 1987, 23, 63.
P. E. Hansen, Prog. Nucl. Magn. Reson. Spectrosc., 1988, 20, 207.
B. L. Zhang, F. Marbon, and M. L. Martin, J. Phys. Org. Chem., 1993, 6, 367.
E. A. Halevi, Prog. Phys. Org. Chem., 1963, 1, 109.
C. Jameson and H. Osten, J. Chem. Phys., 1984, 81, 4293.
M. Oki, Applications of Dynamic NMR spectroscopy to Organic Chemistry in Methods in Stereochemical Analysis, VCH, 1985, 423.
R. C. Neumann, Jr. and V. Jonas, J. Org. Chem., 1974, 39, 925.
H. H. Mantsch, H. Saito, L. C. Leitch, and I. C. P. Smith, J. Am. Chem. Soc., 1974, 96, 256.
W. R. Roth, Tetrahedron Lett., 1964, 1009.
N. M. Sergeyev, Prog. Nucl. Magn. Reson. Spectros., 1975, 9, 71.
D. N. Laikov, Ph.D. Thesis, M. V. Lomonosov Moscow State University, Moscow, 2000 (in Russian).
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Roznyatovsky, V.A., Gerdov, S.M., Grishin, Y.K. et al. Quantitative 2H NMR spectroscopy. 1. Thermodynamic H/D isotope effects in N,N-dimethylformamide and cyclopentadiene molecules. Russian Chemical Bulletin 52, 552–556 (2003). https://doi.org/10.1023/A:1023930000465
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DOI: https://doi.org/10.1023/A:1023930000465