Attachment of the redox-active C-60(H)PPh2 group modulates the electronic structure of the Fe-2 core in [(mu-bdt)Fe-2(CO)(5)(C-60(H)PPh2)]. The neutral complex is characterized by X-ray crystallography, IR, NMR spectroscopy, and cyclic voltammetry. When it is reduced by one electron, the spectroscopic and density functional theory results indicate that the Fe-2 core is partially spin-populated. In the doubly reduced species, extensive electron communication occurs between the reduced fullerene unit and the Fe-2 centers as displayed in the spin-density plot. The results suggest that the [4Fe4S] cluster within the H cluster provides an essential role in terms of the electronic factor.