The cyclic voltammetric behavior of [FeIIICl(salen)] complexes has been investigated in CH3CN and compared to that obtained with [CoII(salen)] analogues. Details of the mechanism associated with iron- and cobalt-salen complex reduction in the presence of the lithium cation have been elucidated by comparison of simulated and experimental voltammograms. Electrogenerated [FeICl(salen)]²⁻ and [FeICl(salophen)]²⁻ complexes catalyze the dehalogenation of halo-alkyl compounds as is the case with [CoI(salen)]⁻ complexes, even in the presence of the lithium cation which allows the reduction to occur at a less negative potential.