锗硅烯与CH<sub>3</sub>OH加成反应机理及区域选择性

引用本文: 曾小兰, 王岩. 锗硅烯与CH₃OH加成反应机理及区域选择性[J]. 物理化学学报, 2015, 31(9): 1699-1707. doi: 10.3866/PKU.WHXB201507202 shu

Citation: ZENG Xiao-Lan, WANG Yan. Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes[J]. Acta Physico-Chimica Sinica, 2015, 31(9): 1699-1707. doi: 10.3866/PKU.WHXB201507202 shu

锗硅烯与CH₃OH加成反应机理及区域选择性

曾小兰 ,
王岩

基金项目:
河南省基础与前沿技术研究计划(142300410194)资助项目 (142300410194)

摘要:

采用密度泛函理论方法, 在B3LYP/6-311++G(d,p)水平, 研究了几种锗硅烯与CH₃OH的加成反应的微观机理和势能剖面, 分析了锗硅烯中Si=Ge双键的极性对加成反应区域选择性的影响. 研究结果表明, 锗硅烯可分别与CH₃OH的单聚体或二聚体发生加成反应. 所有加成反应均从初始亲核或亲电复合物的形成开始. 母体锗硅烯H₂Si=GeH₂与CH₃OH二聚体的加成反应比其与CH₃OH单聚体的相应反应在动力学上更容易些, 但在其它锗硅烯与CH₃OH的反应中情况则相反. 用Ph或SiMe₃基团取代H₂Si=GeH₂中的H原子在动力学上使反应变得不利且SiMe₃基团的影响更显著. 加成反应的区域选择性与锗硅烯中Si=Ge双键的极性以及Si-O(Ge-H)和Ge-O (Si-H)键的相对强弱都有关.

关键词:

English

Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes

ZENG Xiao-Lan ,
WANG Yan

1.
College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, Henan Province, P. R. China
Received Date: 07 May 2015
Available Online: 06 September 2015
Fund Project:
河南省基础与前沿技术研究计划(142300410194)资助项目

Abstract:

Density functional theory (DFT) calculations of the reaction mechanisms and potential energy surfaces for the addition reactions of CH₃OH to several germasilenes were performed at the B3LYP/6-311++G(d,p) level. The effect of the polarity of the Si=Ge double bond in germasilenes on the regioselectivity of the addition reactions was also investigated. The results indicate that germasilenes can react with a monomer or dimer of CH₃OH. All reactions start with formation of nucleophilic or electrophilic complexes. The dimer of CH₃OH adds to H₂Si=GeH₂ kinetically more easily than the monomer. However, the situation is generally the opposite for substituted germasilenes. There is a kinetic disadvantage of substituting phenyl (Ph) or SiMe₃ groups for H atoms in H₂Si=GeH₂ in the addition reactions, and the effect of the SiMe₃ group is more remarkable than that of the Ph substituent. Both the polarity of the Si=Ge double bond and the strength of the Si-O (Ge-H) and Ge-O (Si-H) bonds affect the regioselectivity of the addition reactions.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

锗硅烯与CH₃OH加成反应机理及区域选择性

English

Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes

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Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes

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