Kinetics and Mechanism of the Reaction of Peroxy-compounds with Phosphites, Sulphides, and Aromatic Amines

The studies dealing with the elucidation of the detailed mechanism and quantitative kinetics of the reactions of peroxy-compounds with phosphites, sulphides, and aromatic amines are reviewed. It is shown how evidence has been obtained by ESR of the existence of the one-electron amine oxidation stage, i.e. the stage involving the formation of radical-cations. The consecutive reactions of the radical-cations formed initially and their relation to the behaviour of the amines as polymerisation initiators are analysed. The characteristics of the detection of free radicals in reactions of phosphites and sulphides with hydroperoxides are examined and certain criteria of the latent radical nature of these reactions are formulated. In the last section correlations of the Hammett equation type for rates of the reactions under consideration and also the correlation between the rate constants on the one hand and the ionisation potentials and electron affinities on the other are discussed within the framework of the one-electron oxidation–reduction mechanism.
The bibliography includes 96 references.