Intra- and Intermolecular C−H Activation by Bis(phenolate)pyridineiridium(III) Complexes

A bis(phenolate)pyridine pincer ligand (henceforth abbreviated as ONO) has been employed to support a variety of iridium complexes in oxidation states I, III, and IV. Complexes (ONO)IrL_2Me (L = PPh_3, PEt_3) react with I_2 to cleave the Ir–C bond and liberate MeI, apparently via a mechanism beginning with electron transfer to generate an intermediate Ir(IV) complex, which can be isolated and characterized for the case L = PEt_3. The PPh_3 complex is transformed in benzene at 65 °C to the corresponding phenyl complex, with loss of methane, and subsequently to a species resulting from metalation of a PPh_3 ligand. Labeling and kinetics studies indicate that PPh_3 is the initial site of C–H activation, even though the first observed product is that resulting from intermolecular benzene activation. C–H activation of acetonitrile has also been observed.