In the near past, the chemistry of the organometallic complexes was conventionally established on ligand exchange reactions in which the metal centers comply with the TOLMAN rule of 16-18 valence electrons. The electron transfer catalysis (e.t.c.) of carbon monoxide substitution in cluster compoundsdescribed the use of this new tool in organometallic chemistry for purposes such as ligand exchange, ligand fragmentation, ligand insertion and isomerization. The reaction of Fe2(CO)9 on organic molecules containing the -S-C=S- (motif with sixelectrons) like dithioesterigands leads to the corresponding binuclear complexes, without fragmentation of the organic ligand. In this work, we present the electron transfer catalysis studyin [m-h3(C,S,S)R1C(S)SR2]Fe2(CO)6binuclear complexes in the substitution reaction of a carbonyl with the P(OMe)3 ligand using the control of the electrode potential. Voltammetric behaviors of dithioester ligands, electrochemistry behaviors of their binuclear complexes, electron transfer catalysis of carbonyl substitution reaction, by a ligand L more donor than CO and the kinetic study of the e.t.c. of carbonyl substitution reaction have been studiedin [m-h3(C,S,S)R1C(S)SR2]Fe2(CO)6 binuclear complexes. Our results show that the electron transfer catalysis is an effective way to activate chemical reactions.