Hydridoalkoxycarbonyl complexes of iridium

The synthesis of the cationic complex [Ir(CO)(dmpe)2]+(dmpe = Me2P·CH2·CH2·PMe2) and its reaction with alcohols to form a novel group of hydridoalkoxycarbonyl complexes of iridium(III) of the type [IrH(CO2R)(dmpe)2]+(R = Me or Et) is described. Further reactions of the hydridoalkoxycarbonyl cation to give complexes of the types [IrHCl(dmpe)2]+ and [IrH(CO)(dmpe)2]2+ are also reported. The origin of the unique hydrogen atom has been determined, and tentative structures deduced from spectroscopic measurements have been assigned.