OXIDATIVE ADDITION OF DIALKYLPHOSPHITES TO COMPLEXES OF IRIDIUM(I) AND RHODIUM(I)

Article abstract of DOI:10.1016/0022-328X(83)85073-6

The P-H bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to IrClL2 (L = PPh3, AsPh3) and IrCl(PMe2Ph)3 generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g., IrHClL2<<(MeO)2PO>2H> and IrHCl(PMe2Ph)3.Addition of triphenylphosphine to a solution containing 2 and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh3)2, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh3)2(C5H5N) and IrH(PPh3)2(acac) can be obtained.The ligand arrangements in the various complexes are inferred from IR, 1H and 31P NMR data.