The use of the electron-reservoir complexes [Fe(I)Cp(arene)] for the electrocatalytic synthesis of redox-reversible metal-carbonyl clusters containing ferrocenyldiphenylphosphine

Starting from [M-3(CO)(12)] (M=Fe or Ru) and [CH3CCo3(CO)(9)], the electron -tranfer-chain catalyzed synthesis of new Fe, Ru, and Co carbonyl clusters in which one or several carbonyl ligands have been selectively substituted by one or several ferrocenyldiphenylphosphine (FDPP) ligands has been achie ved using the electron-reservoir complexes [Fe(I)Cp(arene)] as electrocatal ysts. The number of FDPP ligands selectively introduced can be chosen from one per cluster for the three clusters up to one per metal for the Ru and C o clusters. The advantage of this family of electrocatalysts is that the dr iving force for the initiation step can be varied by changing the number of methyl groups on the rings. The FDPP substituted clusters show one reversi ble wave by cyclic voltammetry.