Issue 16, 2004

Dichlorosilane–dimethyl ether aggregation: a new motif in halosilane adduct formation

Abstract

The crystal structures of (H3C)2O, H2SiCl2 and an adduct of these were determined by low-temperature X-ray crystallography on crystals grown in situ at low temperatures on a diffractometer. The adduct of (H3C)2O and H2SiCl2 has the composition [(H3C)2O·H2SiCl2]2 and contains a four-membered Si2O2 ring, with the Cl atoms pointing to the outside and the Si–H functions pointing to the inner side of the ring. The Si2O2 ring has two longer and two shorter Si⋯O bonds and thus deviates from a square. Quantum chemical calculations give a geometry for [(H3C)2O·H2SiCl2]2 which has D2h symmetry and allow to obtain an estimate for the adduct formation energies, which are −13.4 kJ mol−1 for the formation of the mono adduct [(H3C)2O + H2SiCl2 → (H3C)2O·H2SiCl2], −14.4 kJ mol−1 for the dimerization of two mono adducts {(H3C)2O·H2SiCl2 → [(H3C)2O·H2SiCl2]2} and −41.2 kJ mol−1 for the reaction 2 (H3C)2O + 2 H2SiCl2 → [(H3C)2O·H2SiCl2]2. The results are used to rationalize the strongly reduced reactivity of H2SiCl2 towards nucleophilic substitution reactions in (H3C)2O at low temperatures.

Graphical abstract: Dichlorosilane–dimethyl ether aggregation: a new motif in halosilane adduct formation

Article information

Article type
Paper
Submitted
16 Apr 2004
Accepted
29 Jun 2004
First published
21 Jul 2004

Dalton Trans., 2004, 2578-2581

Dichlorosilane–dimethyl ether aggregation: a new motif in halosilane adduct formation

K. Vojinović, U. Losehand and N. W. Mitzel, Dalton Trans., 2004, 2578 DOI: 10.1039/B405684A

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