Cationic complexes of iridium(I) containing phosphites, phosphines, or arsines as ligands

Abstract

A series of four- and five-co-ordinate iridium(I) salts of the type [C₈H₁₂lrL₂]X, [C₈H₁₂lrL₃]X, [lrL₄]X, and [lrL₅]X, (L = tertiary phosphite, phosphine, or arsine; X = BPh₄, PF₆, or ClO₄) have been prepared from the reactions of [C₈H₁₂lrCl]₂ with L. For L = PMe₂Ph the dioxygen adduct [lr(O₂)L₄]BPh₄ has been characterised. The corresponding dioxygen adduct [Ir(O₂)(AsMe₂Ph)₄]BPh₄ has also been prepared. The reactions of [C₈H₁₂IrCl]₂ with L (L = PEt₂Ph and PBuⁿ₃) have given the cis-dihydride, cis-[IrH₂L₄]BPh₄. A new olefin hydride of iridium(III), namely [(C₈H₁₄)₂IrHCl₂]₂, has been isolated. The reaction of this hydride with AsMe₂Ph gave trans-[IrHCl(AsMe₂Ph)₄]PF₆. The ¹H n.m.r. spectra of these salts are discussed.