The reactivity of silanes in free-radical reactions: Analysis in terms of the parabolic model of the transition state |
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Authors: | E T Denisov |
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Institution: | (1) Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russian Federation |
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Abstract: | Rate constants and activation energies of free-radical reactions of silanes and silyl radicals were analyzed in terms of the
parabolic model of the transition state. The kinetic parameters were estimated for 16 groups of reactions of silanes and silyl
radicals. These parameters were used to calculate the activation energies for 112 free-radical reactions and to estimate the
dissociation energies of the Si−H bond for 21 compounds and those of the C−Cl bond for 12 substituted benzyl chlorides. Triplet
repulsion, electronegativity, and radii of atoms of the reaction center of the transition state were shown to play an important
role in the formation of the activation barrier.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1311–1316, July, 1998. |
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Keywords: | activation energy atomic radius bond dissociation energy electronegativity free-radical reactions parabolic model silanes silyl radicals triplet repulsion |
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