Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (9): 1699-1707.doi: 10.3866/PKU.WHXB201507202


Mechanism and Regioselectivity of Addition Reactions of CH3OH to Germasilenes

Xiao-Lan. ZENG,Yan. WANG*()   

  • Received:2015-05-07 Published:2015-09-06
  • Contact: Yan. WANG
  • Supported by:
    Henan Provincial Fundamental and Frontier Technological Research Program, China(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.

Key words: Germasilene, Addition reaction, Reaction mechanism, Density functional theory, Regioselectivity


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