Coordination modes of diphenylphosphinothioformamide in its neutral and deprotonated forms at gold(I)

The reaction of the polydentate ligand Ph2PC(S)N(H)Me with various Au(I) substrates and in different molar ratios leads to complexes with different geometries around the gold center, such as linear mononuclear complexes, [AuCl{Ph2PC(S)N(H)Me}](1), [Au(C6F5){Ph2PC(S)N(H)Me}](2) or [Au{Ph2PC(S)N(H)Me}2]ClO4 (4), linear polynuclear derivatives, [Au2(C6F5)2{Ph2PC(S)N(H)Me}]2(3) and [Au{Ph2PC(SAuCl)N(H)Me}2]ClO4 (6), or the three-coordinate complex [Au{Ph2PC(S)N(H)Me}3]ClO4(5). Treatment of 1 with Tl(acac) produces the deprotonated derivative [Au{Ph2PC(S)NMe}]2(7), which can further react with other gold(I) starting materials leading to the synthesis of [Au2{Ph2PC(S)N(AuX)Me}2](X = Cl (8) and C6F5(9)). The crystal structures of complexes 1, 3, 5 and 7 have been determined by X-ray diffraction studies.