Reactions involving transition metals. Part 13. Reaction of hydroperoxides with complexes of the type trans-[IrX(CO)L2](X = halogen, L = phosphine or arsine)
Abstract
Bis(alkylperoxy)iridium(III) complexes [IrX(O2But)2(CO)L2](X = Cl, L = PPh3, AsPh3, or PPh2Me; X = Br, L = PPh3 or AsPh3) and [IrX(O2CPhMe2)2(CO)L2](X = Cl, L = PPh3 or AsPh3; X = Br, L = PPh3) have been isolated from the reactions of ButO2H or PhMe2CO2H with the respective trans-[IrX(CO)L2] complexes. The similar reactions of ButO2H and PhMe2CO2H with trans-[Irl(CO)(PPh3)2] yield [Irl2(O2R)(CO)(PPh3)2](R = But or PhMe2). The bis(t-butylperoxy)iridium(III) complexes do not themselves catalyse the decomposition of hydroperoxides, polymerisation of styrene, or auto-oxidation of alkenes, but in certain solvents, particularly benzene, a light-induced decomposition reaction occurs to generate radical species which can initiate such reactions.