Thermal and Photochemical Reactions of a Cationic Rhenocene−Acetonitrile Adduct:  The First C−H Bond Activation by Rhenocene Cation

A cationic rhenocene−acetonitrile adduct [Cp₂Re(NCMe)](BF₄) (2) reacted with an excess of benzene and thiophene under UV irradiation to give the C−H bond activation products [Cp₂Re(H)Ph](BF₄) (6) and [Cp₂Re(H)(2-C₄H₃S)](BF₄) (7) in high yields. Deprotonation of 6 proceeded by treatment with DBU to give phenylrhenocene Cp₂RePh (8), while protonation of 8 with HBF₄ regenerated 6.