1825-84-9Relevant academic research and scientific papers
Kinetics of Gas Phase Addition Reactions of Trichlorosilyl Radicals. VIII. Reinvestigation of Addition to Ethylene
Dohmaru, Takaaki,Nagata, Yoshio
, p. 2387 - 2389 (2007/10/02)
The addition of SiCl3 radicals to ethylene has been reinvestigated using a large conversion method.The amended values are log(k3/k5) = -0.17 +/- 0.05 - (0.80 +/- 0.10) kcal mol-1/2.303 RT and log -5/k6 (mol cm-3)> = 3.4 +/- 0.3 - (22.5 +/- 0.7) kcal mol-1/2.303 RT where the reactions involved are radical-SiCl3 + CH3COCH3 (CH3)2-radical-COSiCl3, radical-SiCl3 + C2H4 radical-CH2CH2SiCl3 and radical-CH2CH2SiCl3 + HSiCl3 C2H5SiCl3 + radical-SiCl3.
Kinetics of the Gas-phase Addition Reactions of Trichlorosilyl Radicals. Part 3.-Additions to 2-Olefins
Dohmaru, Takaaki,Nagata, Yoshio
, p. 1141 - 1148 (2007/10/02)
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.
