Electrocatalytic reduction of tert-butyl hydroperoxide at iron electrodes

The electrochemical reduction of tert-butyl hydroperoxide has been investigated in dimethylformamide and 1,2-dichloroethane. Voltammograms at platinum or at glassy carbon electrodes were indistinguishable from the background, whereas at iron electrodes a well-defined cathodic peak was observed. The electrocatalytic reduction of tert-butyl hydroperoxide was enhanced at freshly electrodeposited iron. A study of the reduction mechanism at iron electrode showed that both the electron transfer and the cleavage of the peroxidic bond occurred in a single step, consuming two electrons per mole with the production of tert-butanol. The electrocatalytic effect of iron was also observed for the cumyl hydroperoxide reduction. Organic peroxides are not implicated in an electrocatalytic reduction at iron surfaces.