钠氟类硅烯插入R_H键(R=F,OH,NH_2,CH_3)反应的理论研究  

Theoretical Studies on the Insertion Reaction of Silylenoid H_2SiNaF with R—H(R=F, OH, NH_2, CH_3)

作　　者：王焕杰[1] 解菊[1] 冯大诚[1] 冯圣玉[1] 

机构地区：[1]山东大学化学学院,济南250100

出　　处：《高等学校化学学报》2004年第11期2070-2073,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 3 73 0 3 4)资助

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 .7,1 1 4.6和 1 90 .6k J/ mol(经零点能校正 ) .中间络合物可以解离为取代硅烷和 Na F,这是一个无过渡态的过程 .反应能分别是 -1 2 2 .6,-96.3 ,-6.8和 5 0 .2 k J/ mol.The insertion reaction of silylenoid H 2SiNaF with RH(R=F,OH,NH 2,CH 3) 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.

关 键 词：钠氟类硅烯 插入反应 密度泛函方法 

分 类 号：O641[理学—物理化学]