Photochemical C–H activation and subsequent aerobic oxidation reactions of benzene with Cp*Ir(CO)2

A benzene solution of Cp*Ir(CO)2 was irradiated for 10 h at room temperature, and then the reaction solution was exposed to air overnight, affording two cis–trans isomeric diiridium(Ir–Ir) complexes [Cp*Ir(μ-CO)(Ph)]2 (1 and 4), a mononuclear iridium complex Cp*Ir(CO)(Ph)2 (2), a diiridium(Ir–Ir) complex Cp*2(CO)2Ir2(μ2-C6H4) (3), a novel hexanuclear iridium complex [Cp*2(μ2-Ph)(μ2-H)Ir2](μ3-CO2)[Ir4(CO)11] (5), and trace biphenyl. The molecular structures of complexes 1–5 have been determined by single-crystal X-ray diffraction analysis. Moreover, we studied the reactivities and possible formation paths of some of these complexes.