锡苯和铅苯二聚反应的理论研究  

Theoretical studies on the dimerization reactions of stannabenzenes and plumbabenzenes

作　　者：曾小兰[1] 魏志浩[1] 王岩[1] 

机构地区：[1]信阳师范学院化学化工学院,河南信阳464000

出　　处：《分子科学学报》2015年第1期64-69,共6页Journal of Molecular Science

基　　金：河南省自然科学基金资助项目(142300410194)

摘　　要：采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯.The reaction mechanism dimerization reactions of stannabe functional theory B3LYP method. tial energy surface of the [2 ＋2] and potential energy surface of the [2 ＋2], [4 ＋2] and [4＋ 4] nzenes and plumbabenzenes were investigated by using the density The influences of mesityl substituent at Sn（Pb） atom on the poten- and [4 ＋ 2] reactions were also explored. The results showed that all of studied reactions are concerted processes, and the formation of two C--Sn（Pb） bonds is syn- chronous in most cases. [2 ＋ 2] and [4＋ 2] reactions proceed more easily than corresponding [4 ＋ 4] reaction both thermodynamically and kinetically, while [4 ＋2] path is easier to occur than corre- sponding[2 ＋2] ones kinetically. The mesityl substituent at Sn（Pb） atom has an unfavorable influ- ence on the potential energy surface of [2 ＋ 2]and [4＋ 2] reactions, both thermodynamically and kinetically. Plumbabenzenes are more stable toward dimerization than stannabenzenes thermodynami- cally, although the kinetic reactivity of the former matches that of the latter.

关 键 词：锡苯 铅苯 二聚反应 反应机理 密度泛函理论 

分 类 号：O641[理学—物理化学]