高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (11): 2070.

• 研究论文 • 上一篇    下一篇

钠氟类硅烯插入RH键(R=F,OH,NH2,CH3)反应的理论研究

王焕杰, 解菊, 冯大诚, 冯圣玉   

  1. 山东大学化学学院, 济南250100
  • 收稿日期:2004-01-20 出版日期:2004-11-24 发布日期:2004-11-24
  • 基金资助:

    国家自然科学基金(批准号:20373034)资助

Theoretical Studies on the Insertion Reaction of Silylenoid H2SiNaF with R—H(R=F, OH, NH2, CH3)

WANG Huan-Jie, XIE Ju, FENG Da-Cheng, FENG Sheng-Yu   

  1. College of Chemistry, Shandong University, Jinan 250100, China
  • Received:2004-01-20 Online:2004-11-24 Published:2004-11-24

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摘要： 用密度泛函方法研究了钠氟类硅烯插入R_H键(R=F,OH,NH2,CH3)的反应机理.4个反应的机制类似,反应经历了类硅烯的亲电接近、亲核插入和取代三个阶段之后,形成中间络合物,4个反应的势垒分别为0.9,61.7,114.6和190.6kJ/mol(经零点能校正).中间络合物可以解离为取代硅烷和NaF,这是一个无过渡态的过程.反应能分别是-122.6,-96.3,-6.8和50.2kJ/mol.

关键词: 钠氟类硅烯, 插入反应, 密度泛函方法

Abstract: The insertion reaction of silylenoid H2SiNaF with RH(R=F,OH,NH2,CH3) was studied at B3LYP/6-31G* level by using density functional theory. The mechanism of these four reactions was analogical. The reaction goes through three stages: electrophilic approach, nucleophilic insertion and substitution, then the intermediate formed. Accounting to zero-point vibration energy, the potential barriers of the four reactions are 0.9, 61.7, 114.6 and 190.6 kJ/mol respectively. The intermediate could dissociate to substituent silane and NaF. This dissociating process has no transition state. The reaction energies for the four reactions are -122.6, -96.3, -6.8 and 50.2 kJ/mol respectively.

Key words: Silylenoid H2SiNaF, Insertion reaction, Density functional theory

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