Issue 4, 1982
From the journal:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases

Kinetics of the gas-phase addition reactions of trichlorosilyl radicals. Part 3.—Additions to 2-olefins

Takaaki Dohmaru  and  Yoshio Nagata  

Abstract

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)2ĊOSiCl3(3), ·SiCl3+[double bond splayed left]C[double bond, length as m-dash]C[double bond splayed right]⇌[double bond splayed left]Ċ—[graphic omitted]—SiCl3(5, –5), and [double bond splayed left]—[graphic omitted]—SiCl3+ HSiCl3→ H[graphic omitted]—[graphic omitted]SiCl3+·SiCl3(6), [graphic omitted].

The rate parameters of reaction (5) are expressed per reaction site; an asterisk indicates the site of addition in an unsymmetrical olefin. Evaluated 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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Article information

DOI
https://doi.org/10.1039/F19827801141
Article type
Paper

J. Chem. Soc., Faraday Trans. 1, 1982,78, 1141-1148

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Kinetics of the gas-phase addition reactions of trichlorosilyl radicals. Part 3.—Additions to 2-olefins

T. Dohmaru and Y. Nagata, J. Chem. Soc., Faraday Trans. 1, 1982, 78, 1141 DOI: 10.1039/F19827801141

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