Cryoelectrochemical study of the cleavage of radical anions of diiron and diruthenium carbonyl dimers

Abstract

Electrochemical reduction of the diiron complexes [Fe(CO) 2 (η 5 -Cp)] 2 and [Fe(CO) 2 (η 5 -Cp * )] 2 proceeds at room temperature by two electrons, but at low temperature is a one-electron reaction producing dimer radical anions that are stable on the voltammetric time scale. Analysis of the reaction kinetics at intervening temperatures shows that the two-electron reaction occurs through the radical anion, which dissociates to a mononuclear anion and a radical. The second electron is delivered homogeneously to the radical by a second dimer radical anion