Abstract
(DMF)2(HCl)3 and (DMF)2(HCl)4 heterocomplexes were studied for the first time in terms of the B3LYP/6-31++G(d, p) density functional calculation. The resulting data about their structure, stability, strength of intermolecular bonds, and degree of proton transfer in O...H...Cl bridges are compared with the results of a similar calculation fulfilled for (DMF)m(HCl)n clusters (m, n = 1–2) and with the experimental data on the structure and properties of acid-base complexes in DMF solutions of HCl. An extremely stable symmetrical cycle of four molecules — (DMF)2(HCl)2 — is assumed to be a structure-forming element of solution in the DMF-HCl system in the range of concentrations achievable under normal conditions. When [HCl]0 > [DMF]0, the “excess” hydrogen chloride molecules add to the chlorine atoms of this cycle, forming heterocomplexes with a branched structure. Addition of more HCl molecules to the (DMF)2(HCl)2 cycle appreciably increases the degree of proton transfer from acid to base molecule.
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Original Russian Text Copyright © 2005 by G. V. Yukhnevich, E. G. Tarakanova, O. J. Tsoy, N. B. Librovich, and I. S. Kislina
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Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 18–25, January–February, 2005.
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Yukhnevich, G.V., Tarakanova, E.G., Tsoy, O.J. et al. Structure of (DMF)m(HCl)n complexes (m= 2, n = 3–4). J Struct Chem 46, 16–22 (2005). https://doi.org/10.1007/s10947-006-0003-7
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DOI: https://doi.org/10.1007/s10947-006-0003-7