物理化学学报 >> 2010, Vol. 26 >> Issue (12): 3345-3350.doi: 10.3866/PKU.WHXB20101225

量子化学及计算化学 上一篇    下一篇

双[1,2-二(三氟甲基)乙烯-1,2-二硫基]镍与丁二烯反应的溶剂效应

孙丽丽1,2, 赵月红1, 韩清珍1, 温浩1   

  1. 1. 中国科学院过程工程研究所多相复杂系统国家重点实验室, 北京100190;
    2. 中国科学院研究生院, 北京100049
  • 收稿日期:2010-07-07 修回日期:2010-08-20 发布日期:2010-12-01
  • 通讯作者: 温浩 E-mail:hwen@home.ipe.ac.cn
  • 基金资助:

    国家自然科学基金(20703047, 20821092)资助项目

Solvent Effect in the Reaction between Bis[1,2-di(trifluoromethyl) ethylene-1,2-dithiolato] Nickel and Butadiene

SUN Li-Li1,2, ZHAO Yue-Hong1, HAN Qing-Zhen1, WEN Hao1   

  1. 1. State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, P. R. China;
    2. Graduate University of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • Received:2010-07-07 Revised:2010-08-20 Published:2010-12-01
  • Contact: WEN Hao E-mail:hwen@home.ipe.ac.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20703047, 20821092).

摘要:

采用密度泛函理论(DFT) 在B3LYP/6-31G(d) 水平上研究了双[1,2- 二( 三氟甲基) 乙烯-1,2- 二硫基]镍Ni[S2C2(CF3)2]2)与丁二烯的反应机理. 采用极化连续介质模型(PCM), 考察了溶剂对各反应驻点的电荷分布、偶极矩、溶剂化自由能的影响. 计算结果表明: Ni[S2C2(CF3)2]2与丁二烯的反应为前线轨道对称性匹配的协同反应, 溶剂介电常数的增大有利于稳定各反应驻点. 同时在同种溶剂中, 过渡态和产物稳定的程度大于反应物, 从而反应更加容易进行.

关键词: 密度泛函理论, 双[1,2-二(三氟甲基)乙烯-1,2-二硫基]镍, 丁二烯, 溶剂效应

Abstract:

We studied the reaction mechanism for the reaction between bis[1,2-di(trifluoromethyl) ethylene-1,2-dithiolato] nickel (Ni[S2C2(CF3)2]2) and butadiene by density functional theory (DFT) at the B3LYP/6-31G(d) level. The solvent effect on the charge distribution, dipole moment, and solvation free energies of the stationary points were investigated using the polarizable continuum model (PCM). The calculation results showed that this reaction was orbital symmetry allowed and concerted. The reaction stationary points become more stable with an increase of solvent dielectric constant. Additionally, the degree of stabilization for the transition state and the product is larger than that of the reactants in the same solvent, which means that the reaction occurs more easily.

Key words: Density functional theory, Bis[1,2-di(trifluoromethyl)ethylene-1,2-dithiolato] nickel, Butadiene, Solvent effect

MSC2000: 

  • O641