New Systematic Route to Mixed-Valence Triiron ClustersDerived from Dinuclear Models of the Active Site of [Fe–Fe]-Hydrogenases.

A novelreaction pathway to synthesize the linear trinuclear clusters[Fe3(CO)5(κ2-diphosphine)(μ-dithiolate)2] via the direct reaction of the dinuclear hexacarbonyl precursor[Fe2(CO)6(μ-dithiolate)] with the mononuclearspecies [Fe(CO)2(κ2-diphosphine)(κ2-dithiolate)] has been developed with diphosphine (dppe) anddithiolate (pdt = propanedithiolate) (1) or adtBn({SCH2}2NBn = azadithiolate) (2). A crystallographic study was carried out on 2andMössbauer spectroscopy, and DFT calculations have been usedto describe the electronic and structural properties of 1. The electrochemical properties of 1in the absenceand in the presence of a weak acid have been the subject of a preliminaryinvestigation. [ABSTRACT FROM AUTHOR]