硅烯对含氢氯硅烷选择性Si—X键插入反应的理论研究  

Selective Insertion Reaction of Silylene into Si—X Bond of Hydrochlorosilane

作　　者：杨雪敏[1] 金娟[1] 徐征[1] 李志芳[1] 邱化玉[1] 蒋剑雄[1] 来国桥[1] 

机构地区：[1]杭州师范大学有机硅化学及材料技术教育部重点实验室,浙江杭州310012

出　　处：《杭州师范大学学报（自然科学版）》2013年第1期14-20,共7页Journal of Hangzhou Normal University(Natural Science Edition)

基　　金：国家青年科学基金项目(20903032);浙江省自然科学基金项目(Y4090470)

摘　　要：采用密度泛函B3LYP/6-31++G(d,p)算法,比较了通过位阻效应稳定的二烷基取代硅烯和通过电子效应稳定的二氨基取代硅烯对含氢氯硅烷Si—X(X=H或Cl)键插入反应的反应选择性差异.研究结果表明:(1)二氨基取代硅烯的Si—X键插入反应的反应活性低且放热不明显,产物在热力学上远不及二烷基取代硅烯的产物稳定;(2)二氨基取代硅烯对二甲基氢氯硅烷(Me2SiHCl)表现出了与二烷基取代硅烯不同的反应选择性,Si—Cl插入反应优先于Si—H插入反应.其根本原因在于Si—H插入反应过渡态能量的稳定性对硅烯的亲电性作用的依赖性显著大于Si—Cl插入反应.Calculating the potential energy surface of the insertion reaction of σ bond among three silylenes and four silane/chlorosilane modle moleculars, the paper studied the reaction selectivity for steric stabilzed dialkylsilylene and electronic stabilized diaminosilylene insertion into Si-X （X= H, Cl） bond of hydrochlorosilanes by B3LYP/6-31 ＋ ＋ G（d, p） method. The results indicate that the reactivity of diaminosilylene is apparently lower, and the reaction is less exothermic. The Si-Cl insertion is preferred to the Si H insertion, the reason of which is that the stabilization of transition state energy in Si--H insertion reaction has more dependence on the electrophilicity of silylene than Si-Cl insertion reaction. The stronger dependence of Si-H insertion barrier to silylene＇s electrophilicity is considered as the main reason.

关 键 词：理论计算 硅烯 含氢氯硅烷 Si—X插入反应 

分 类 号：O64[理学—物理化学]