Beiträge zur Chemie der Halogensilan‐Addukte, 20. Hexakoordinierte Verbindungen von Trichlorsilanen. – Darstellung, Kristall‐und Molekülstruktur von RSiCl3·bipy

Abstract
Hexacoordinated Compounds of Trichlorosilanes. – Preparation, Crystal and Molecular Structure of BSiCl3·bipyThe octahedral Si complexes CHCl2SiCl3·bipy (1), CCl3SiCl3·bipy (2), and Cl3SiCCl2SiCl3·bipy (3) are obtained by the reaction of the respective trichlorosilanes and 2.2′‐bipyridine (bipy). Their composition is independent of the initial ratio of the components. X‐ray structure determinations show the Si atoms of all three complexes to be octahedrally coordinated with the substituted methyl groups in axial positions. The configurations represent structures of least steric hindrance assuming spheric substituents and demonstrate the usefulness of this structural model for solid compounds (in contrast possibly to dissolved compounds) even for substitutents deviating strongly from this assumption. Bond lengths and angles agree with the presence of hexacoordinated complexes. Deviations from expected values are interpreted in terms of considerable steric interactions. 3 represents a case of strongly hindered coordination requiring interesting steric adjustments.

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