Journal of the Chemical Society. Perkin transactions II p. 1162 - 1165 (1980)
Update date:2022-08-17
Topics:
Baker, Richard H.
Haszeldine, Robert N.
Robinson, Peter J.
The gas-phase thermal isomerisation of trichloro-(1,1-difluoroethyl)silane (I) to chloro-(1,1-dichloroethyl)difluorosilane (II) is a first-order homogeneous process at 375-416 K and 11-67 mmHg initial pressure.The reaction is unaffected by the presence of the radical inhibitors 2,3-dimethylbut-2-ene and nitric oxide, and it is concluded that the rate-determining step is a unimolecular isomerisation of (I) to dichloro-(1-chloro-1-fluoroethyl)fluorosilane (III), which then undergoes a secondary fast isomerisation to the observed product (II).The a transition state in which the fluorine atom transfer is more advanced than the chlorine atom transfer.The minor products vinyl chloride and dichlorodifluorosilane are shown to arise from thermal and chemically activated decomposition of the initially formed (II) and/or (III).
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