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Physicochemical aspects of isomerisation of free radicals

Evgenii Timofeevich Denisov 1
Evgenii Timofeevich Denisov
, 
Taisa Grigor'evna Denisova 1
Taisa Grigor'evna Denisova
1 Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, Chernogolovka, Moscow region
Published 30 November 2003
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Denisov E. T., Denisova T. G. Physicochemical aspects of isomerisation of free radicals // Russian Chemical Reviews. 2004. Vol. 73. No. 11. pp. 1091-1119.
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Denisov E. T., Denisova T. G. Physicochemical aspects of isomerisation of free radicals // Russian Chemical Reviews. 2004. Vol. 73. No. 11. pp. 1091-1119.
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TY - JOUR
DO - 10.1070/RC2004v073n11ABEH000880
UR - https://rcr.colab.ws/publications/10.1070/RC2004v073n11ABEH000880
TI - Physicochemical aspects of isomerisation of free radicals
T2 - Russian Chemical Reviews
AU - Denisov, Evgenii Timofeevich
AU - Denisova, Taisa Grigor'evna
PY - 2004
DA - 2003/11/30
PB - ANO Editorial Board of the journal Uspekhi Khimii
SP - 1091-1119
IS - 11
VL - 73
ER -
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@article{2004_Denisov,
author = {Evgenii Timofeevich Denisov and Taisa Grigor'evna Denisova},
title = {Physicochemical aspects of isomerisation of free radicals},
journal = {Russian Chemical Reviews},
year = {2004},
volume = {73},
publisher = {ANO Editorial Board of the journal Uspekhi Khimii},
month = {Nov},
url = {https://rcr.colab.ws/publications/10.1070/RC2004v073n11ABEH000880},
number = {11},
pages = {1091--1119},
doi = {10.1070/RC2004v073n11ABEH000880}
}
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Denisov, Evgenii Timofeevich, and Taisa Grigor'evna Denisova. “Physicochemical aspects of isomerisation of free radicals.” Russian Chemical Reviews, vol. 73, no. 11, Nov. 2004, pp. 1091-1119. https://rcr.colab.ws/publications/10.1070/RC2004v073n11ABEH000880.
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Abstract

Kinetic data on intramolecular abstraction of hydrogen atoms in alkyl, alkoxyl and peroxyl radicals are generalised and analysed. It is shown that the activation energies of these reactions are affected by ring strain. The kinetic parameters of mono- and bimolecular elimination reactions are compared. The difference between the activation energies of these reactions is interpreted using the model of intersecting parabolas. The same model is used to discuss the results of analysis of cyclisation of alkyl radicals; the ring strain energy is shown to play an important role in the activation of these reactions. It is noted that the difference between the electron affinities of the C, N and O atoms is clearly manifested in the cyclisation of aminyl and ω-formylalkyl radicals. The kinetic parameters of cyclisation and bimolecular radical addition reactions are compared. The experimental data on the transfer of the vinyl and aryl groups in alkyl radicals are analysed.