The preparation and reactions of nitrato-complexes of iridium(III) containing tertiary phosphines or tertiary arsines as ligands

Abstract

Complexes of type IrX₂(NO₃)L₃(X = halogen, L = PMe₂Ph, PEt₂Ph, AsMe₂Ph) have been prepared. The nitrate ligand is readily displaced by neutral ligands, Q, to give cations of type [IrX₂QL₃]⁺(Q = CO, PMe₂Ph, AsMe₂Ph, pyridine, 3-methylpyridine, 4-methylpyridine or NH₃). Complexes of type [IrX₂(CO)L₃]⁺, with two different configurations, were prepared. [IrCl₂(CO)L₃]⁺ reacts with NaOMe to give IrCl₂(CO₂Me)L₃. Complexes of the types IrCl₂Y (PMe₂Ph)₃ with Y = OH, NO₂, N₃ or OMe were also prepared. The methoxide complex on heating gives a quantitative yield of the hydride IrHCl₂(PMe₂Ph)₃. Complexes of type [IrHQ₂(PMe₂Ph)₃]²⁺(Q = pyridine or CO; Q₂= 1,10-phenanthroline were also prepared). The configurations of the complexes were determined from their ¹H (methyl) n.m.r. and i.r. spectra.