二锗烯与几种亲核试剂加成反应的计算研究  

Computational Study on the Addition Reactions ofDigermene with Several Nucleophilic Reagents

作　　者：曾小兰[1] 郁宁宁 王岩[1] ZENG Xiaolan;YU Ningning;WANG Yan(College of Chemistry and Chemical Engineering,Xinyang Normal University,Xinyang 464000,China)

机构地区：[1]信阳师范学院化学化工学院,河南信阳464000

出　　处：《信阳师范学院学报（自然科学版）》2020年第4期543-548,共6页Journal of Xinyang Normal University(Natural Science Edition)

基　　金：国家自然科学基金项目(21876143)。

摘　　要：采用密度泛函理论方法研究了二锗烯(H 2Ge=GeH 2)与几种亲核试剂(CH 3OH、C 4H 9OH、PhOH及CF 3OH)的加成反应的微观机理和势能剖面,考查了几种亲核试剂的加成反应活性.计算结果表明,H 2Ge=GeH 2与CH 3OH、C 4H 9OH或PhOH的单聚体的加成反应均有两种不同的反应途径,即亲核加成和亲电加成,且亲电加成相对更容易发生.但H 2Ge=GeH 2与CH 3OH的二聚体及三聚体的加成反应只能以亲核加成的方式进行.CH 3OH二聚体作为亲核试剂的反应活性高于相应的单聚体,但C 4H 9OH二聚体的加成反应活性低于其单聚体.CH 3OH、C 4H 9OH、PhOH及CF 3OH作为亲核试剂的反应活性从高到低依次为:CH 3OH>C 4H 9OH>PhOH>CF 3OH.The mechanism and potential energy profile of the addition reactions between digermene(H 2Ge=GeH 2)and several nucleophilic reagents(CH 3OH,C 4H 9OH,PhOH and CF 3OH)were studied by using density functional theory(DFT),and the addition reactivity of these reagents was explored.The computed results show that the addition reactions between H 2Ge=GeH 2 and monomer of CH 3OH,C 4H 9OH or PhOH can occur in two different ways,i.e.,nucleophilic addition and electrophilic addition,and electrophilic addition is relatively easier to happen.However,the addition reactions of H 2Ge=GeH 2 with dimer or trimer of CH 3OH can proceed only by nucleophilic addition.The reactivity of the CH 3OH dimer as a nucleophile is higher than that of the corresponding monomer,but the addition activity of the C 4H 9OH dimer is lower than that of the monomer.The order of reactivity of CH 3OH,C 4H 9OH,PhOH and CF 3OH as nucleophilic reagents from high to low is as follows:CH 3OH>C 4H 9OH>PhOH>CF 3OH.

关 键 词：二锗烯 亲核试剂 加成反应 反应性 

分 类 号：O641[理学—物理化学]