Synthesis and characterization of new intramolecular C-H activated Rhodium(III) and Iridium(III) complexes containing functionalized triphenylphosphines

The hemilabile tertiary phosphine ether and phosphine ester compounds o-Ph2 PC6H4CH2OMe (DPBE) and o-Ph2PC6H4CH2OC(O)Et (DPES) and their reactions with different Rh(I) and Ir(I) precursor complexes have been investigated. It i s shown that both DPBE and DPES are capable of undergoing oxidative metal i nsertions at the benzylic positions with the displaced protons appearing as apical hydride ligands in the resulting octahedral complexes. The solution structures of all oxidative addition adducts have been unambiguously ident ified by various NMR techniques. Also, single-crystal X-ray diffraction stu dies have been performed for the complexes [RhCl(2,5-NBD)(DPES)] and [IrH(1 ,5-COD)(DPES)[BF4].