The coordination of the S-based anions, thiophenoxide (PhS^-, a), ethyl xanthogenate (EtOCS₂^-, b), 2-mercaptopyridinate (pyS^-, c), and 2-mercaptopyrimidinate (pymS^-, d), to the central platinum atom of the trinuclear Pt(III)₂,Pt(II) complex [(C₆F₅)₂Pt^III(μ-PPh₂)₂Pt^III(μ-PPh₂)₂Pt^II(C₆F₅)₂](Pt-Pt), 1, gives rise to three different types of complexes: (i) the Pt(II),Pt(II),Pt(II) complex [NⁿBu₄][(C₆F₅)₂Pt^II(μ-PPh₂)₂Pt^II{κ²-S,P-μ-(PhS)PPh₂}(μ-PPh₂)Pt^II(C₆F₅)₂], 2a; (ii) the Pt(II),Pt(IV),Pt(II) mixed valence complexes [NⁿBu₄][(C₆F₅)₂Pt^II(μ-PPh₂)₂Pt^IV(κ²-S,S'-EtOCS₂)(μ-PPh₂)₂Pt^II(C₆F₅)₂], 3b, and [NⁿBu₄][(C₆F₅)₂Pt^II(μ-PPh₂)₂Pt^IV{κ²N,P-(pymS)PPh₂}(μ-PPh₂)₂Pt^II(C₆F₅)₂], 3d; and (iii) the Pt(II),Pt(II),Pt(II) derivatives [NⁿBu₄][(C₆F₅)₂Pt^II(μ-PPh₂)₂Pt^II{κ²N,P-μ-(pyS)PPh₂}(μ-PPh₂)Pt^II(C₆F₅)₂], 4c, and [NⁿBu₄][(C₆F₅)₂Pt^II(μ-PPh₂)₂Pt^II{κ²N,P-μ-(pymS)PPh₂}(μ-PPh₂)Pt^II(C₆F₅)₂], 4d. Complexes 2a, 4c, and 4d display new Ph₂P(SL) ligands stemming from the reductive coupling of a PPh₂ group and the S-based anions. Complex 2a exhibits a κ²-S,P bridging coordination mode while 4c and 4d exhibit a κ²-N,P mode in the solid state. In acetone solution, an equilibrium between the κ²-N,P and the κ²-S,P forms was ascertained for complexes with 2-mercaptopyrimidinate and 2-mercaptopyridinate by NMR techniques. Complex 4d evolved, in acetone solution at 323 K, to the Pt(II),Pt(II),Pt(II) complex [NⁿBu₄][(C₆F₅)₂Pt^II(μ-PPh₂){κ²-P,N-μ-(Pym)PPh₂}Pt^II(κ²-S,P-μ-SPPh₂)(μ-PPh₂)Pt^II(C₆F₅)₂], 5d. The X-ray diffraction structures of the trinuclear complexes 3'b (the complex having the same anion as 3b but Ph₃P-N-PPh₃⁺ as the countercation instead of NⁿBu₄) and 4d are described.