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Dissociative electron transfer between arene radical anions and halogenoalkanes: a pulse radiolysis study

1994; Royal Society of Chemistry; Volume: 90; Issue: 1 Linguagem: Inglês

10.1039/ft9949000075

1364-5455

James Grimshaw, John R. Langan, G. Arthur Salmon,

Electrochemical Analysis and Applications

Rate constants have been determined at room temperature (20 ± 1 °C) for a number of examples of the dissociative electron-transfer reaction between arene radical anions and the haloalkanes 1-iodobutane, 2-iodo-2-methylpropane and 2-bromo-2-methylpropane in the organic amide solvents N-methylpyrollidin-2-one N,N′-dimethylformamide. The data, when combined with the results of other workers using electrochemical techniques, indicate a linear relationship between log(kET) and the reduction potential of the donor radical anion (E°D) spanning eight orders-of-magnitude of kET up to the diffusion-controlled limit. The effect of temperature on kET was investigated for the reactions of 1-iodobutane with a number of the radical anions.The factors which affect the rates of these reactions and the success of current theory in explaining them are discussed.