Electron Delocalization from the Fullerene Attachment to the Diiron Core within the Active-Site Mimics of [FeFe]Hydrogenase

Attachment of the redox-active C60(H)­PPh2 group modulates the electronic structure of the Fe2 core
in [(μ-bdt)­Fe2(CO)5(C60(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 Fe2 core is partially spin-populated.
In the doubly reduced species, extensive electron communication occurs
between the reduced fullerene unit and the Fe2 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.