Theoretical Study on the Thermodynamic Hydricity of Imidazole-based Organic Hydrides in Acetonitrile

doi:10.3969/j.issn.0251-0790.2012.02.011

Abstract

Abstract: Theoretical thermodynamic hydricities of imidazole-based hydrides in acetonitrile were calculated by different methods. Compared with the available experimental values, it was found that the MP2/6-311++G^**//B3LYP/6-31+G^* protocol with the IEF-PCM(interval equation formalism-polarized continuam model) solvent model could predict the thermodynamic hydricity with a good precision. With this method, the thermodynamic hydricities of 14 imidazole-based organic hydrides(IHs) in acetonitrile were estimated. The results show that all of the properties of substituent, the aromatization ability of IH after releasing a hydride anion, the contribution from the frontier orbital of the 2-phenyl of imidazole to the whole frontier orbital of IH and IC(the cation of IH), the natural bond orbital(NBO) charge distribution and the solvent effect have influences on the thermodynamic hydricities of imidazole-based hydrides in acetonitrile.

Key words: Hydride, Imidazole, Thermodynamic hydricity, Theoretical calculation, IEF-PCM model

CLC Number:

O621.16

TrendMD:

YU Ao, WANG Hui-Kai, XUE Xiao-Song, CAI Yu, WANG Yong-Jian, HE Jia-Qi. Theoretical Study on the Thermodynamic Hydricity of Imidazole-based Organic Hydrides in Acetonitrile[J]. Chem. J. Chinese Universities, 2012, 33(02): 276.

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