Bifurcate Hydrogen Bonds. Interaction of Intramolecularly H-Bonded Systems with Lewis Bases

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• 作者：Valery F. Sidorkin ; Evgeniya P. Doronina ; Nina N. Chipanina ; Tamara N. Aksamentova ; Bagrat A. Shainyan
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：July 10, 2008
• 年：2008
• 卷：112
• 期：27
• 页码：6227 - 6234
• 全文大小：326K
• 年卷期：v.112,no.27(July 10, 2008)
• ISSN：1520-5215

文摘

The structure and the hydrogen bonding in the systems formed by the intramolecularly H-bonded systems, namely, maltol (3-hydroxy-2-methyl-4-pyrone), 5, 2,4,6-trinitrophenol, 6, acetylacetone enol, 7, with Lewis bases, phosgene, 8, dioxane, 9, and DMSO, 10, have been studied by density functional theory (B3LYP) and MP2 using the 6-311G* basis set. The continuum solvent effect was simulated by IEF-PCM model. The hydrogen bond analysis using the atoms in molecules (AIM) method was applied by using the MP2(full)/6-311++G** electron density to establish the nature of the bifurcate hydrogen bond (BHB) in these systems as well as contributory factors for its stabilization. The nature of interaction in the intermolecular H-complexes formed by compounds 5−7 with the Lewis bases 8−10 was shown to depend on the strength of the intramolecular hydrogen bond O···H and the strength of the base. The critical values of the Cf">O···H and Nf">O···H angles for which the formation of BHB is possible, have been determined.