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Journal of Organometallic Chemistry 636 (2001) 148156 www.elsevier.com/locate/jorganchem
 

Summary: Journal of Organometallic Chemistry 636 (2001) 148156
www.elsevier.com/locate/jorganchem
Are disilacyclopropylidenes and their carbenoids good precursors
for the unknown 1,3-disilaallenes?
Nadejda Sigal, Yitzhak Apeloig *
Department of Chemistry and the Lise Meitner-Miner6a Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology,
Haifa 32000, Israel
Received 3 April 2001; accepted 1 May 2001
This paper is dedicated to Professor O.M. Nefedov, one of the pioneers of low-valent organic and silicon compounds, on the occasion of his
70th birthday
Abstract
Ring opening of disilacyclopropylidenes provides a possible route to the yet unknown 1,3-disilaallenes. To examine the
feasibility of this reaction we studied computationally the potential energy surfaces for the elimination of LiCl from cyclo-
CSi2H4ClLi (and for comparison also for cyclo-C3H4ClLi), which serve as models for the corresponding substituted systems. On
the basis of ab initio molecular orbital calculations at the MP2/6-31G(d)//MP2/6-31G(d)+ZPE level we predict that the
activation energy for the conversion of cyclo-CSi2H4ClLi to 1,3-disilaallene (+LiCl) is only 6.5 kcal mol-1
, making this reaction
a promising strategy for the synthesis of 1,3-disilaallenes. This barrier is much smaller than the barrier (42.5 kcal mol-1
) for the
all carbon analogue, cyclo-C3H4ClLi. The differences between the silicon and carbon systems are discussed. 2001 Elsevier

  

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

 

Collections: Chemistry