Kinetics of the Gas-phase Addition Reactions of Trichlorosilyl Radicals. Part 3.-Additions to 2-Olefins
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Source and publish data:
Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1141 - 1148 (1982)
Update date:2022-08-10
Topics:
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Authors:
Dohmaru, Takaaki
Nagata, Yoshio
Article abstract of DOI:10.1039/f19827801141
The following Arrhenius parameters for the forward and reverse steps of trichlorosilyl radical additions to trans-but-2-ene, cis-but-2-ene, cis-pent-2-ene, 2-methyl-but-2-ene and cyclopentene have been obtained by a competitive method.The relevant elementary reactions are .SiCl3 + CH3COCH3 --> (CH3)2C.OSiCl3 (3) .SiCl3 + >C=C< <==> >C.-C-SiCl3 (5,-5) and >C.-C-SiCl3 + HSiCl3 --> HC-C-SiCl3 + .SiCl3 (6).
The rate parameters of reaction (5) are expressed per reaction site; an asterisk indicates the site of addition in an unsymmetrical olefin.Evaluted values of A-5 and A5 imply a fairly 'loose' transition state in reaction (5).The Si-C bond energy has been estimated. .SiCl3 radicals have been revealed to be electrophilic and susceptible to steric hindrance.
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Full text of DOI:10.1039/f19827801141
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