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

• THEORETICALAND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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 E-mail:wangyanxytc@163.com
  • Supported by:
    Henan Provincial Fundamental and Frontier Technological Research Program, China(142300410194)

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

MSC2000: 

  • O641