A Pentanuclear Mixed Gold(III)-Silver(I) Phosphide with an Unusual T-Frame µ3-Cl Bridge

The reaction of the mixed gold(III)-silver(I) diphenylphosphide complex [Au(C 6F 5) 2(μPPh 2) 2Ag] 2 (1) with an equimolecular amount of [AgCl(PPh 3) 2] leads to the formal insertion of the latter into 1, affording the pentanuclear derivative [{Au(C 6F 5{(μ-PPh 2AgPPh 3}(μ-PPh 2)} 2(μ-Ag)(μ 3-Cl)] (2). Surprisingly, complex 2 is also obtained by treatment of [Au(C 6F 5) 2-(PPh 2H) 2]ClO 4 with [Ag(TfO)(PPh 3)] (TfO = trifluoromethanesulfonate) and AgTfO (2:2:1) in the presence of PPN(acac) (PPN = [N(PPh 3) 2] +, acac = acetylacetonate) and PPNCl. The crystal structure of 2 has been determined by X-ray diffraction studies, and it displays an unusual, perfectly planar T-frame μ 3-Cl atom acting as a bridge between the three silver atoms