Some oxidative addition reactions of halogenocarbonyliridium(I) complexes of the type trans-[IrX(CO)L2](L = tertiary phosphine or tertiary arsine)

Abstract

Oxidative addition reactions of hydrogen, oxygen, methyl halides, substituted-methyl halides, acyl halides, sulphonyl halides, carbon disulphide phenyldiazonium tetrafluoroborate or tetracyanoethylene to complexes of the type trans-[IrX(CO)L₂](X = halide, L = PMe₃, PMe₂Ph, PEt₂Ph, or AsMe₂Ph) are described. The ¹H (methyl) n.m.r. spectrum of the PMe₂Ph complexes gives the stereochemistry of the adduct. In benzene solution the addition of MeBr or Mel to [IrCl(CO)(PMe₂Ph)₂] is trans; the addition of acetyl chloride or acetyl bromide is similarly trans. Near- and far-i.r. data for the complexes formed are discussed, particularly the effects of trans-ligands on iridium–chlorine stretching frequencies.