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Rate constants for the reactions of CCl(X2II) with a series of silanes

✍ Scribed by F.C. James; H.K.J. Choi; O.P. Strausz; T.N. Bell

Publisher: Elsevier Science
Year: 1979
Tongue: English
Weight: 381 KB
Volume: 68
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(79)80084-6

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✦ Synopsis

Rate constants for the gas phase reactions of CC1 generated by the flash photolysis of CHBrzCl with a series of silanes have been obtained by kinetic absorption spectroscopy. In general, the rate constants arc very high, and range fmm (4 8 2 0.5) X 10' (SIHH~) to (6-4 r 0.34) % IO9 for SitHe. CC1 does not insert into the Si-C or primary C-H bonds of silanes and its nte of reaction with tertiary 5-H bonds is 600 times greater than with tertiary C-H bonds. CC1 reacts slowly with the Si-Si bond. kH/k~ varies from 1.9 to 1.0 on gomg fmm primary to tertiary Si-H bonds. The electrophilic character of CC1 is manifested, on a per Si-H bond basis, by ew_xIIent correIations between the rate constants and the hydridic character of the Si-H bond, and betxkeen logk and the ionization potential.

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