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.