Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Theoretical Studies Gas Phase Reaction of Alkoxide-Exchange at Silicon and Carbon Centers$^\dag$

  • Lee, Ik-Choon (Department of Chemistry, Inha University) ;
  • Yang, Ki-Yull (Department of Chemistry, Inha University) ;
  • Park, Byong-Seo (Department of Materials Engineering, Suncheon National College) ;
  • Lee, Kae-Soo (Department of Chemistry, Chonnam National University)
  • Published : 1986.06.20
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Abstract

MNDO and ab initio calculations for gas phase reactions of alkoxide-exchange at silicon and carbon centers have been performed. Results show that MNDO values of ${\Delta}$E's of these reactions closely parallel those of the STO-3G method. The alkoxide-exchange at silicon is shown to be facile due to the formation of stable five-coordinate intermediate while the reaction at carbon is predicted to proceed with high barrier; the difference in this substitution behavior between carbon and silicon is shown to be due to an easy valence shell expansion of silicon in accommodating an extra bond in the formation of stable five-coordinate intermediates.

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