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The reactivity of silanes in free-radical reactions: Analysis in terms of the parabolic model of the transition state

  • Physical Chemistry
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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.

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Authors and Affiliations

  1. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, 142432, Chernogolovka, Moscow Region, Russian Federation

    E. T. Denisov

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  1. E. T. Denisov
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1311–1316, July, 1998.

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Denisov, E.T. The reactivity of silanes in free-radical reactions: Analysis in terms of the parabolic model of the transition state. Russ Chem Bull 47, 1274–1279 (1998). https://doi.org/10.1007/BF02495546

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  • DOI: https://doi.org/10.1007/BF02495546

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