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

Abstract

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(k_ET) and the reduction potential of the donor radical anion (E^°_D) spanning eight orders-of-magnitude of k_ET up to the diffusion-controlled limit. The effect of temperature on k_ET 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.