Synthesis of homo- and hetero-polynuclear coinage metal complexes of 2-(diphenylphosphino)aniline

Abstract

The reaction of the asymmetric ligand 2-(diphenylphosphino)aniline (PNH₂) with gold(I), silver(I) or copper(I) substrates in various molar ratios leads to the complexes [M(PNH₂)₂]A (M = Au, A = TfO (1); M = Ag, A = TfO (2), ClO₄ (3); M = Cu, A = TfO (4)), the homodinuclear derivatives [M(PNH₂)]₂A₂ (M = Ag, A = TfO (7), ClO₄ (8); M = Cu, A = TfO (9)) or [M(PNH₂)₃]A (M = Au, A = TfO (12); M = Ag, A = ClO₄ (13); M = Cu; A = TfO (14)). Reaction of [AuCl(PNH₂)] with AgClO₄ (1∶1) in acetone causes the ligand to condense with the solvent, resulting in the synthesis of [Au(PNCMe₂)]₂(ClO₄)₂ (5). Treatment of the gold(I) compound 1 with the same silver(I) or copper(I) starting materials as before gives the heteronuclear species [AuM(PNH₂)₂](TfO)₂ (M = Ag (10); M = Cu (11)). The optical properties of some of these complexes have been studied and the crystal structures of compounds 5, 10 and 12 have been determined by X-ray diffraction.