高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (10): 1711.

• 研究论文 • 上一篇    下一篇

BH2+与C2H2反应势能面的量子化学研究

屈正旺, 李泽生, 丁益宏, 孙家钟   

  1. 吉林大学理论化学研究所理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:2000-08-02 出版日期:2001-10-24 发布日期:2001-10-24
  • 通讯作者: 屈正旺(1971年出生),男,博士,从事物理化学研究.E-Mail:qzwzhh@263.net E-mail:qzwzhh@263.net
  • 基金资助:

    国家自然科学基金(批准号:29733100;29892168)资助

Quantum-chemical Investigation on the Potential Energy Surface of the Reaction of BH2+ with C2H2

QU Zheng-Wang, LI Ze-Sheng, DING Yi-Hong, SUN Chia-Chong   

  1. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, China
  • Received:2000-08-02 Online:2001-10-24 Published:2001-10-24

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摘要： 用B3LYP/6-311G(d,p)密度泛函方法和高级电子相关的CCSD(T)/6-311G(2df,p)偶合簇法研究BH+2与C2H2反应势能面.结果表明:该势能面上存在(a)H2B+·C2H2,(b)HBCHCH2+,(c)H2BCCH2+和(d)H2·BHCCH+2+通过对C2H2的分步亲电加成以及随后的氢迁移和H2消除等反应形成离解产物HBCCH2++H2,该反应不需要活化能且大量放热.计算结果有助于深入了解BH2+等缺电子硼氢正离子的反应行为.

关键词: 硼氢正离子, 势能面, 反应机理

Abstract: The potential energy surface of the ion-molecular reaction of BH2+ with C2H2 in gas-phase has been investigated theoretically by using the B3LYP/6-311G(d,p) and the high-level electron-correlation CCSD(T)/6-311G(2df,p) single-point levels. Four isomers H2B+·C2H2(a), HBCHCH2+(b), H2BCCH2+(c) and H2·BHCCH+(d) are found, among which isomer (b) is the most stable both thermodynamically and kinetically while isomers (a), (c) and (d) are kinetically unstable. The mechanism for the reaction BH+-2+C2H2→HBCCH++H2 is discussed based on the potential energy surface. It is shown that BH2+ may carry out an electrophilic addition towards C2H2 followed by multi-step H-shifts and final H2-elimination to form product HBCCH++H2, the total reaction is barrier-free and largely exothermic. The calculated results presented in this paper may be helpful for understanding the chemical behavior of electron-deficient borohydride cations such as BH2+.

Key words: Borohydride cation, Potential energy surface, Reaction mechanism

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