The outcome of the reaction of the Pt(III),Pt(III) complex [(C 6 F 5) 2 Pt III (µ-PPh 2) 2 Pt III (C 6 F 5) 2 ](Pt-Pt) (1) with the S-based anions thiophenoxide (PhS-), ethyl xanthogenate (EtOCS 2-), 2-mercaptopyrimidinate (pymS-) and 2-mercaptopyridinate (pyS-) was found dependent on the reaction solvent. The reactions carried out in acetone led to the formation of [N n Bu 4 ][(R F) 2 Pt II (μ-PhS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (2), [N n Bu 4 ][(R F) 2 Pt II (μ-EtOCS 2-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (3), [N n Bu 4 ][(R F) 2 Pt II (μ-pymS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (4) or [N n Bu 4 ][(R F) 2 Pt II (μ-pyS-PPh 2)(μ-PPh 2)Pt II (R F) 2 ] (5), respectively (R F = C 6 F 5). Complexes 2-5 display new Ph 2 P(SL) ligands exhibiting a κ 2-P,S bridging coordination mode, which derive from a reductive elimination of a PPh 2 group and the S-based anion. Carrying out the reaction in dichloromethane afforded, in the cases of EtOCS 2 and pymSmonobridged complexes [N n Bu 4 ][(PPh 2 R F)(R F) 2 Pt II (μ-PPh 2)Pt II (EtOCS 2)(R F)] (6) and [N n Bu 4 ][(PPh 2 R F)(R F) 2 Pt II (μ-PPh 2)Pt II (pymS)(R F)] (7), respectively, which derive from a reductive elimination of a PPh 2 group with a pentafluorophenyl ring. The reaction of 1 with EtOCS 2 K 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 EtOCS 2 K in acetone; b) the transformation of 1 into the neutral complex [(PPh 2 R F)(CH 3 CN)(R F)Pt II (μ-PPh 2)Pt II (R F) 2 (CH 3 CN)] (8), which, on turn, reacts with EtOCS 2 K 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 2 crystallisation with n-hexane. The XRD structures of 2, 3, 4, 6, 7 and 8 were determined and the behaviour in solution of the new complexes is discussed.