高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (5): 876.

• 研究论文 • 上一篇    下一篇

过渡金属离子与烷烃反应机理的理论研究──镍离子(2D)与丙烷反应中氢分子的还原消除机理

张冬菊, 张长桥, 刘成卜   

  1. 山东大学理论化学研究所, 济南 250100
  • 收稿日期:2001-03-22 出版日期:2002-05-24 发布日期:2002-05-24
  • 通讯作者: 刘成卜(1948年出生),男,教授,博士生导师,主要从事量子化学与分子反应动力学研究.E-mail:cbliu@sdu.edu.cn E-mail:cbliu@sdu.edu.cn
  • 基金资助:

    山东省自然科学基金重大项目(批准号:Z2000B02)资助.

Theoretical Studies of the Mechanism and Energetics for the Reactions of Transition Metal Ions with Alkanes──H2 Elimination Mechanism in the Reaction of Ni+(2D) with Propane

ZHANG Dong-Ju, ZHANG Chang-Qiao, LIU Cheng-Bu   

  1. Institute of Theoretical Chemistry, Shandong University, Jinan 250100, China
  • Received:2001-03-22 Online:2002-05-24 Published:2002-05-24

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摘要： 以Ni+与C3H8反应作为过渡金属离子与烷烃反应的范例体系,用B3LYP密度泛函方法计算了[Ni,C3,H8]+基态势能面上各驻点的构型、频率和能量,结果表明,该反应的H2分子消除需经历两个基元步骤,即Ni+首先插入一级或二级C-H键,然后经H转移过渡态异构化为较稳定的中间体,继而解离产生H2分子.计算的反应热为142.28kJ/mol,与相应的实验值(127.85kJ/mol)符合较好.

关键词: 过渡金属离子, 烷烃, 反应机理, 密度泛函理论

Abstract: The reaction of Ni+ with propane have been studied extensively by using density functional theory,and the detailed information regarding the mechanism and energetics of H2 elimination on the potential energy surface of [Ni,C3,H8]+ have been obtained at B3LYP/6-311 + +G(3df/,3pd) level.Both the initial primary or secondary C—H bond activations in propane mediated by Ni+ in the reaction of Ni+ with propane can result in the H2 elimination from Ni(C3H8)+ .Five intermediates, two C—H bond activation transition states and three H-shift transition states are located on this potential energy surface.The heat ofreaction for Ni++C3H8→Ni(C3H6)++H2 is calculated to be 142.28 kj/mol.This result is in goodagreement with the experimental finding, a value of 127.85 kJ/mol at 0 K.

Key words: Transition metal ion, Alkanes, Reaction mechanism, Density functional theory

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