高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (02): 276.doi: 10.3969/j.issn.0251-0790.2012.02.011

• 有机化学 • 上一篇    下一篇

咪唑类化合物在乙腈溶液中负氢解离焓的理论研究

于奡1, 王会凯1, 薛小松1, 蔡余1, 王永健2, 何家骐1   

  1. 1. 南开大学化学学院, 中心实验室, 天津 300071;
    2. 南开大学生命科学学院, 生物活性材料教育部重点实验室, 天津 300071
  • 收稿日期:2011-05-03 出版日期:2012-02-10 发布日期:2012-01-13
  • 通讯作者: 于 奡, 男, 博士, 副研究员, 主要从事有机化合物结构与性能研究. E-mail: esr@nankai.edu.cn 王永健, 女, 博士, 教授, 主要从事生物活性材料研究. E-mail: yongjian_wang@nankai.edu.cn E-mail:esr@nankai.edu.cn;yongjian_wang@nankai.edu.cn
  • 基金资助:

    国家"九七三"计划项目(批准号: 2011CB606202)和国家自然科学基金(批准号: 511730083)资助.

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

YU Ao1, WANG Hui-Kai1, XUE Xiao-Song1, CAI Yu1, WANG Yong-Jian2, HE Jia-Qi1   

  1. 1. Central Laboratory, College of Chemistry, Nankai University, Tianjin 300071, China;
    2. Key Laboratory of Bioactive Materials, Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071, China
  • Received:2011-05-03 Online:2012-02-10 Published:2012-01-13

摘要: 在与实验对照的基础上优化出一套计算咪唑类化合物在乙腈溶液中负氢解离焓的理论方法, 即MP2/6-311++G(d,p)//B3LYP/6-31+G(d)结合IEF-PCM溶剂模型及UA0孔穴计算法. 在此基础上, 有目的地设计了14种咪唑类负氢给体, 并计算了其在乙腈溶液中的负氢解离焓, 系统分析了影响其负氢解离焓的各种因素. 结果表明, 取代基的电子效应、体系释放负氢后的芳构化能力、咪唑环2位的苯基对前线分子轨道的贡献程度、体系电荷的分布情况及溶剂化效应等多种因素均能影响咪唑负氢给体在乙腈溶液中的负氢解离焓.

关键词: 负氢给体, 咪唑化合物, 负氢解离焓, 理论计算, IEF-PCM模型

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

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