Kinetics of the Gas-phase Addition Reactions of Trichlorosilyl Radicals. Part 3.-Additions to 2-Olefins

DOI: 10.1039/f19827801141

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

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Authors:

Dohmaru, Takaaki

Nagata, Yoshio

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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.

Full text of DOI:10.1039/f19827801141

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