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

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: 7 May 2015
Available Online: 20 July 2015
Fund Project: 河南省基础与前沿技术研究计划(142300410194)资助项目 (142300410194)

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.
- Germasilene,
- Addition reaction,
- Reaction mechanism,
- Density functional theory,
- Regioselectivity
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Mechanism and Regioselectivity of Addition Reactions of CH₃OH to Germasilenes