The outcome of the reaction of the Pt(III),Pt(III) complex [(C₆F₅)₂Pt^III(μ-PPh₂)₂Pt^III(C₆F₅)₂](Pt-Pt) (1) with the S-based anions thiophenoxide (PhS^-), ethyl xanthogenate (EtOCS₂^-), 2-mercaptopyrimidinate (pymS^-), and 2-mercaptopyridinate (pyS^-) was found to be dependent on the reaction solvent. The reactions carried out in acetone led to the formation of [NⁿBu₄][(R_F)₂Pt^II(μ-PhS-PPh₂)(μ-PPh₂)Pt^II(R_F)₂] (2), [NⁿBu₄][(R_F)₂Pt^II(μ-EtOCS₂-PPh₂)(μ-PPh₂)Pt^II(R_F)₂] (3), [NⁿBu₄][(R_F)₂Pt^II(μ-pymS-PPh₂)(μ-PPh₂)Pt^II(R_F)₂] (4), and [NⁿBu₄][(R_F)₂Pt^II(μ-pyS-PPh₂)(μ-PPh₂)Pt^II(R_F)₂] (5), respectively (R_F = C₆F₅). Complexes 2-5 display new Ph₂P(SL) ligands exhibiting a ?²-P,S bridging coordination mode, which is derived from a reductive elimination of a PPh₂ group and the S-based anion. Carrying out the reaction in dichloromethane afforded, in the cases of EtOCS₂^- and pymS^-, the monobridged complexes [NⁿBu₄][(PPh₂R_F)(R_F)₂Pt^II(μ-PPh₂)Pt^II(EtOCS₂)(R_F)] (6) and [NⁿBu₄][(PPh₂R_F)(R_F)₂Pt^II(μ-PPh₂)Pt^II(pymS)(R_F)] (7), respectively, which are derived from reductive elimination of a PPh₂ group with a pentafluorophenyl ring. The reaction of 1 with EtOCS₂K in acetonitrile yielded a mixture of 3 and 6 as a consequence of the concurrence of two processes: (a) the formation of 3 by a reaction that parallels the formation of 3 by 1 plus EtOCS₂K in acetone and (b) the transformation of 1 into the neutral complex [(PPh₂R_F)(CH₃CN)(R_F)Pt^II(μ-PPh₂)Pt^II(R_F)₂(CH₃CN)] (8), which, in turn, reacts with EtOCS₂K to give 6. The 1 to 8 transformation was found to be fully reversible. In fact, dissolving 8 in acetone or dichloromethane afforded pure 1 after solvent evaporation or crystallization with n-hexane. The XRD structures of 2-4 and 6-8 were determined, and the behavior in solution of the new complexes is discussed.