The chloro-bridged dimer [(PC)Pt(mu-Cl)(2) (PC = [((Bu2P)-Bu-t-o-C6H4)-CMe2](-)) reacts with silver(I) acetate to yield the monomeric kappa(2)-acetate complex ((PC)Pt(kappa(2)-OOCMe)]. Its trifluoroacetate analogue exists in solution as a mixture of the monomer and two isomeric dimers, and crystallizes as the approximately C-2-symmetrical dimer [(PC)Pt(mu-OOCCF3)](2). NMR experiments and density functional theory calculations show that the monomeric species are favored by bulky ligands and electron-rich carboxylates. [(PC)Pt(OOCCF3)] undergoes a ligand-dehydrogenation reaction in hot trifluoroacetic acid to yield [(PCC)Pt(OOCCF3)(2)] (PCC = ((BU2P)-B-t-o-C6H4)-C(Me)=CH2).