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JOURNALS // Uspekhi Khimii // Archive

Usp. Khim., 2004 Volume 73, Issue 11, Pages 1181–1209 (Mi rcr491)

This article is cited in 32 papers

Physicochemical aspects of isomerisation of free radicals

E. T. Denisov, T. G. Denisova

Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow region

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.

Received: 30.10.2003

DOI: 10.1070/RC2004v073n11ABEH000880


 English version:
Russian Chemical Reviews, 2004, 73:11, 1091–1119

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