AbstractThe reaction between tris(acetylacetonato)magnanese(III) and hexa(N,N‐dimethylformamide)iron(III) perchlorate in acetonitrile proceeds in two stages. The first stage corresponds to the reaction of pentacoordinated Fe(DMF) 53+with Mn(acac)3, and the rate‐determining step of the second stage consists mainly in the elimination of a DMF ligand from Fe(DMF) 63+to yield Fe(DMF) 53+which reacts rapidly with the manganese complex. The formation of Fe(DMF) 53+is catalyzed by Mn(acac)3, this catalytic effect being decreased by manganese products. The rate‐determining step for the formation of Fe(acac)3is the transfer of the first acetylacetonate to yield Fe(acac)2+. The final products of iron depend on the ratio of reactant concentrations. With Mn or Fe in excess, Fe(acac)3or Fe(acac)2+are ma