Abstract
The tautomerization energies for the reaction R2P(O)H ⇄ R2P-OH, where R= OH, OCH3, OC2H5, CH3, and CF3, have been calculated by the CNDO/2 method with optimization of the exponents of the Slater 3d AO's according to the criterion of a minimum total energy for the molecule. The results are in qualitative agreement with the experimental data. The MNDO and CNDO/2 calculations with the use of a standard sp basis predict greater stability for the structures with a three-coordinate phosphorus atom, in contradiction to experiment.
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Literature cited
M. I. Kabachnik, “Tautomerism of some organophosphorus compounds,” in: Chemistry and Application of Organophosphorus Compounds [in Russian], Nauka, Moscow (1957), pp. 18–41.
G. O. Doak and L. D. Freedman, “The structures and properties of the dialkyl phosphonates,” Chem. Rev., 61, No. 1, 31–44 (1961).
M. S. Gordon, J. A. Boatz, and M. Shmidt, “Ab initio studies of HXYPO and XYPOH molecules,” J. Phys. Chem., 88, No. 14, 2998–3000 (1984).
W. J. Pietro and W. J. Hehre, “Tautomerization of dimethyl phosphonate,” J. Am. Chem. Soc., 104, No. 13, 3594–3595 (1982).
V. M. Mamaev, I. P. Gloriozov, V. V. Orlov, and Yu. V. Babin, “Calculation of the geometric and electronic structure of Mg porphyrins in optimal spd' basis sets,” Dokl. Akad. Nauk SSSR, 282, No. 6, 1437–1441 (1985).
Yu. A. Ustynyuk, V. M. Mamaev, Yu. V. Babin, and I. P. Gloriozov, “Development of the CNDO/2 method for calculating the structure of compounds of third-row elements,” ibid., 292, No. 3, 674–677 (1987).
C. A. Coulson, “d Electrons and molecular bonding,” Nature, 221, No. 5186, 1106–1109 (1969).
M. S. Gordon and M. S. Korth, “Second-row molecular orbital calculations. 5. A minimal basis INDO for Na-Cl,” J. Am. Chem. Soc., 100, No. 9, 2670–2678 (1978).
G. M. Zhidomirov, A. A. Bagatur'yants, and I. A. Abronin, Applied Quantum Chemistry [in Russian] (1979).
D. P. Santry and G. A. Segal, “Approximate self-consistent molecular orbital theory. 4. Calculations of molecules including the elements sodium through chlorine,” J. Chem. Phys., 47, No. 1, 158–174 (1967).
F. Grein and K. Weiss, “Molecular complexes: a modified CNDO study of benzene-borazine systems,” Theor. Chim. Acta, 34, No. 4, 315–326 (1974).
M. Kondo, I. Ando, R. Dhujo, and A. Nishioka, “Theoretical calculations of carbon-13 NMR shielding constants and their tensors in hydrocarbons by the finite perturbation method,” J. Magn. Reson., 24, No. 3, 315–326 (1976).
V. A. Naumov and L. V. Vilkov, Molecular Structures of Organophosphorus Compounds [in Russian], Nauka, Moscow (1986).
M. J. S. Dewar and W. Thiel, “Ground states of molecules. 38. The MNDO method. Approximation and parameters,” J. Am. Chem. Soc., 99, No. 15, 4899–4907 (1977).
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 4, pp. 486–490, July–August, 1989.
In conclusion, we express our thanks to V. L. Foss for showing an interest in this work and for some valuable discussions.
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Babin, Y.V., Mamaev, V.M., Ustynyuk, Y.A. et al. Quantum-chemical investigation of tautomerism of hydrophosphoryl compounds. Theor Exp Chem 25, 450–454 (1990). https://doi.org/10.1007/BF00530441
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DOI: https://doi.org/10.1007/BF00530441