A two-center model of the concerted molecular decomposition of unsaturated compounds |
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Authors: | E T Denisov and T S Pokidova |
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Institution: | 1.Institute of Problems of Chemical Physics,Russian Academy of Sciences,Chernogolovka, Moscow oblast,Russia |
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Abstract: | A semiempirical model of the concerted decomposition of unsaturated compounds (olefins, alcohols, acids, and ethers) and aliphatic
esters into two molecules is suggested. The model considers the decomposition reaction as a single-step transfer of the hydrogen
atom in one reaction center and the dissociation of a C-C or C-O bond in the other accompanied by a shift of π electrons in
the cyclic six-membered transition state. Each elementary event in such a concerted reaction is characterized by its own activation
energy, E
abs for the transfer of H, E
>d
for bond dissociation, and E
π for the shift of π bonds. The E
abs and E
d
activation energies were calculated by the method of intersecting parabolas. The spectrum of activation energies (sets of
the E
abs, E
d
, and E
π values) for each of 45 decomposition reactions was calculated with the use of experimental data. The contribution of enthalpy
to the activation energy of each event was estimated. |
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Keywords: | |
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