Abstract
Geometric parameters, values of force constants and vibration frequencies for different geometric configurations of enolic and ketonic forms of molecules of β-diketones, R″COCH2COR′ (R″ and/or R′ are H, CH3, CF3) have been computed by the ab initio method MO LCAO SCF using wide bases of Cartesian Gaussians. The enolic form of the considered molecules is most energetically favorable. Values of isomerization energy, the height of internal rotation barriers, and energies of the intramolecular hydrogen bond were obtained for it. The stabilization of the enolic form was shown to be caused by the presence of the intramolecular hydrogen bond in the chelate ring. The effect of a substituent on the computed values of molecular parameters was examined. The comparison with the available experimental data testifies to a sufficiently high reliability of the data obtained.
Similar content being viewed by others
References
V. V. Sliznev, S. B. Lapshina, and G. V. Girichev, Zh. Strukt. Khim., 42, No. 4, 631–644 (2001).
V. V. Sliznev, S. B. Lapshina, and G. V. Girichev, ibid., 43, No. 1, 51–60 (2002).
A. H. Lowrey, C. George, P. D’Antonio, and J. Karle, J. Am. Chem. Soc., 93, No. 24, 6399–6403 (1971).
T. Chiavassa, P. Verlaque, L. Pizzala, and P. Roubin, Spectrochim. Acta., 50A, No. 2, 343–351 (1994).
K. Nishikawa, Y. Ohta, T. Yoshimoto, et al., J. Mol. Struct., 615, 13–22 (2002).
M. A. Rios and J. Rodriguez, J. Mol. Struct. (Theochem.), 228, 149–158 (1991).
A. A. Granovsky, http://www.classic.chem.msu.su/gran/gamess/index.html.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, et al., J. Comput. Chem., 14, No. 11, 1347–1363 (1993).
A. D. Becke, J. Chem. Phys., 98, 5648–5652 (1993).
P. J. Stephens, F. J. Devlin, C. F. Chablowski, and M. J. Frisch, J. Phys. Chem., 98, 11623–11627 (1994).
R. H. Hertwig and W. Koch, Chem. Phys. Lett., 268, 345–351 (1997).
S. Huzinaga, J. Chem. Phys., 42, No. 4, 1293–1302 (1965).
T. H. Dunning, ibid., 55, No. 2, 716–723 (1971).
M. Urban, V. Kello, and P. Carsky, Theor. Chim. Acta (Berl.), 55, 205 (1977).
P. C. Hariharan and J. A. Pople, ibid., 28, 213 (1973).
Author information
Authors and Affiliations
Additional information
Original Russian Text Copyright © 2006 by V. V. Sliznev, S. B. Lapshina, and G. V. Girichev
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 228–239, March–April, 2006.
Rights and permissions
About this article
Cite this article
Sliznev, V.V., Lapshina, S.B. & Girichev, G.V. Ab initio study of the structure of enolic and ketonic forms of β-diketones with the general formula R″COCH2COR′ (R′ and R″ = H, CH3, CF3). J Struct Chem 47, 220–231 (2006). https://doi.org/10.1007/s10947-006-0290-z
Received:
Issue Date:
DOI: https://doi.org/10.1007/s10947-006-0290-z