Photochemical Intermolecular Oxidative Addition of the C−Cl Bond of Chlorobenzene to Rhenium

The phenyl chloride complexes Cp*Re(CO)(L)(Ph)Cl (L = P(OEt)3 (6), Pc (7), P(OMe)3 (8), and PMe2Ph (9)) have been prepared by irradiation of the corresponding rhenium dinitrogen complex Cp*Re(CO)(L)(N2) in chlorobenzene. In the case of L = P(OPh)3 the result was instead the formation of the cyclometalated complex Cp*Re(CO){η2-P(OC6H4)(OPh)2}H (10), arising from intramolecular C−H oxidative addition of a phenyl group of the phosphine oxide ligand.