J. Kobayashi, Kazunori Ishida, T. Kawashima
Sep 1, 2002
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Journal
Silicon Chemistry
Abstract
A trichlorosilane bearing a tetradentate ligand with three coordinating arms was synthesized by the reaction of triarylmethyllithium with tetrachlorosilane. Its heptacoordinate structure around the central silicon atom has been revealed by X-ray crystallographic analysis. Three methoxy oxygen atoms are located at the opposite side to the chlorine atoms,and the average Si ··· O interatomic distance is 2.807Å, shorter than the sum of van der Waals radii (Si··· O: 3.40 Å). Chlorine atoms on the central silicon atom were not replaced by any nucleophiles such as alkyllithium, hydride anion, and alcohols. Effective suppression of nucleophilic attack is attributed to the intramolecular interactions of lone pairs of oxygen atoms with σ*Si−Cl antibonding orbital aswell as steric hindrance.