Physicochemical aspects of isomerisation of free radicals
文献情報
Evgenii T. Denisov, Taisa G. Denisova
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. The bibliography includes 146 references.
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掲載誌
Russian Chemical Reviews
Founded in 1932, Russian Chemical Reviews aims to publish timely and important review articles covering most aspects of modern chemistry, including: Chemical physics Physical chemistry Computational and theoretical chemistry Catalysis Coordination chemistry Analytical chemistry Organic, organometallic and organoelement chemistry Chemistry of macromolecules Applied chemistry Biochemistry, bio-organic chemistry and biomolecular chemistry Medicinal chemistry Materials chemistry, nanochemistry, nanostructures Environmental chemistry
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