Photoinduced Ligand-to-Metal Charge Transfer of Cobaltocene: Radical Release and Catalytic Cyclotrimerization.

Irradiation of cobalt metallocenes at the ligand-to-metal charge transfer energies results in the labilization of the cyclopentadienyl-cobalt bond and radical release. The cyclopentadienyl radical is detected by electron paramagnetic resonance (EPR) spectroscopy using a spin trap and can also be chemically trapped using hydrogen-atom-donating reagents. This reaction presents a new photochemical method of generating new cobalt complexes or of forming cyclopentadienyl cobalt(I) species that are active for catalytic [2 + 2 + 2] cyclotrimerization reactions. More importantly, these results also show that cobaltocene should not be considered as a photostable redox reagent under many conditions, including those relevant to photovoltaics or photocatalysis.