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A New Method for the Synthesis of Branched Polysilane Yitzhak Apeloig,* Michael Yuzefovich, Michael Bendikov, and
 

Summary: A New Method for the Synthesis of Branched Polysilane
Anions
Yitzhak Apeloig,* Michael Yuzefovich, Michael Bendikov, and
Dmitry Bravo-Zhivotovskii*
Department of Chemistry and the Minerva Center for Computational Quantum Chemistry,
Technion-Israel Institute of Technology, 32000 Haifa, Israel
Karl Klinkhammer
Institute fur Anorganische Chemie der Universitat Stuttgart, Pfaffenwaldring 55,
D-70550 Stuttgart, Germany
Received August 26, 1996X
Lithiation by MeLi of three families of branched polysilanes (Me3Si)3Si-X {(1) X ) SiMe2H,
t-BuMe2Si, SiMe2SiMe3, t-BuSiMe2SiMe2; (2) X ) SiMe(SiMe3)2, Si(SiMe3)3, SiMe2Si(SiMe3)3,
SiMeHSi(SiMe3)3; (3) X ) Si(SiMe3)2Cl, Si[Si(SiMe3)3]MeCl, Si[Si(SiMe3)3]HCl} yields,
depending on X, one of the following: (a) novel branched polysilyllithium compounds; (b)
the known (Me3Si)3SiLi; (c) various mixtures. The cleavage of family 1 can be understood
in terms of steric effects, i.e., assuming that MeLi attacks preferentially the sterically less
hindered Si atom leading to the formation of new polysilyllithium compounds, e.g., t-BuMe2-
Si(Me3Si)2SiLi,3THF and t-BuMe2SiSiMe2(Me3Si)2SiLi,3THF, which were isolated in a
crystalline form. The X-ray structure of the former is presented. In contrast to 1 the
lithiation of the branched polysilanes 2 leads exclusively (mostly with (Me3Si)3SiSiMe-

  

Source: Apeloig, Yitzhak - Department of Chemistry, Technion, Israel Institute of Technology

 

Collections: Chemistry