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

Abstract

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.