Molecular structures of various alkyldichlorosilanes in the solid state

Dalton Transactions : an International Journal of Inorganic Chemistry
Jörg Wagler, Robert Gericke

Abstract

A series of organodichlorosilanes RR'SiCl2(R,R' = (CH2)3; (CH2)4; (CH2)5; Me,Me; Me,H; Me,Cl) was studied by single-crystal X-ray diffraction analyses. At ambient temperature liquid chlorosilanes (melting points in the range of 180-220 K) were transferred into glass capillaries and crystallized in situ on a diffractometer. In the solid state structure these chlorosilanes are monomeric, even in the case of the sterically less demanding 1,1-dichlorosilacyclobutane (CH2)3SiCl2. Interestingly, regardless the steric demand of the alkyl substituents, the dialkyldichlorosilanes exhibit essentially the same Cl-Si-Cl angle (for (CH2)3SiCl2, (CH2)4SiCl2, (CH2)5SiCl2, Me2SiCl2: 106.08(3)°, 106.07(4)°/105.86(4)°, 106.91(2)° and 105.59(6)°, respectively). Replacement of one alkyl group by hydrogen has only a marginal influence on the Cl-Si-Cl angle (MeHSiCl2106.31(3)°), whereas in MeSiCl3slightly wider Cl-Si-Cl angles are found (ranging between 107.04(11)° and 107.86(11)°), in accordance with VSEPR. Computational analyses, i.e., potential energy surface scans of the Cl-Si-Cl angle variation, of (CH2)3SiCl2, Me2SiCl2, MeHSiCl2and H2SiCl2reveal essentially identical energy profiles for the Cl-Si-Cl deformation in these four dichlorosilanes wi...Continue Reading

References

Mar 11, 2000·Acta Crystallographica. Section C, Crystal Structure Communications·J BuschmannM Rottger
Aug 11, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Krunoslav VojinovićNorbert W Mitzel
Jan 26, 2006·Acta Crystallographica. Section B, Structural Science·Roman GajdaAndrzej Katrusiak
Nov 9, 2007·Acta Crystallographica. Section C, Crystal Structure Communications·Uwe Böhme, Ines C Foehn
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick

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