Alkoxide-ion attack at the nitrosyl group of [IrCl3(NO)(PPh3)2]+ to give alkyl nitrite complexes of iridium(III)

The cationic nitrosyls, [IrCl3(NO)L2]+(L = PPh3, AsPh3) react with alcohols to give neutral iridium(III) complexes containing bound alkyl nitrites, IrCl3(RONO)L2(R = Me, Et, Pr). These reactions parallel the formation of complexes containing alkoxycarbonyl groups as ligands by alkoxide-ion attack on cationic carbonyl complexes. The nitrite complexes revert to the parent nitrosyls with acids and it is suggested that this reaction bears upon the mechanism of formation of nitrosyl complexes in the frequently used preparations which make use of alkyl nitrites, N-nitroso-reagents, nitrous acid, and NO+ salts. New routes to the dinitrosyl cations, [Ir(NO)2L2]+, and preparations of Ir(NO)(AsPh3)3, are also reported.