高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (9): 1530.

• 研究论文 • 上一篇    下一篇

气相离子-分子反应B2H3-+CS2——B2H3S-+CS的理论研究

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:2000-06-30 出版日期:2001-09-24 发布日期:2001-09-24
  • 通讯作者: 屈正旺(1971年出生),男,博士,从事物理化学研究.
  • 基金资助:

    国家自然科学基金(批准号:29892168)资助

Theoretical Study on the Gas Phase Reaction: B2H3-+CS2B2H3S-+CS

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:2000-06-30 Online:2001-09-24 Published:2001-09-24

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摘要： 用密度泛函方法B3LYP/6-311++G(d,p)和高级电子相关的偶合簇法CCSD(T)/6-311++G(d,p)研究了气相离子-分子反应B2H3-+CS2B2H3S-+CS的机理.结果表明,B2H3最可能进攻CS2中碳原子形成三元环中间体,随后通过氢迁移和最终消除CS的反应步骤形成硫原子转移产物H3BBS-+CS,反应大量放热且不需要活化能.B2H3直接对CS2中硫原子进攻夺取硫原子的反应方式存在一定能垒阻碍.计算结果有助于深入了解B2H3,B3H-6和B4H7-等缺电子硼氢负离子的反应行为.

关键词: 硼氢负离子, 离子-分子反应, 反应机理

Abstract: The mechanism for the gas phase ion molecule reaction B2H - 3+CS2B2H3S-+CShas been investigated theoretically by using the B3LYP/6311++G( d,p ) and the high level electron correlation CCSD(T)/6311++G( d,p ) single point levels. It is shown that the B2H3- anion may attack the carbon atom of CS2 to form a three membered ring intermediate followed by a Hshift and subsequently a CSextrusion steps to reach the final dissociation product H3BBS-+CS. The reaction is largely exothermic and no activation energy is needed for this three membered ring mechanism. On the other hand, an activation barrier is found for the sulfur atom abstraction reaction initiated by the sulfur attack of B2H3- towards CS2. The calculated results presented in this paper may be helpful for understanding the chemical behavior of electron deficient boron hydride anions such as B2H3-, B3H6- and B4H7- , etc..

Key words: Borohydride anion, Ion molecule reaction, Reaction mechanism

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