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

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)](2)A(2) (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(PN=CMe2)](2)(ClO4)(2) (5). Treatment of the gold(I) compound 1 with the same silver(i) or copper(l) 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.