Mononuclear Platinum(II) Complexes Incorporating κ²-Carboxylate Ligands: Synthesis, Structure, and Reactivity

The chloro-bridged dimer [(PC)Pt(μ-Cl)]2 (PC = [(tBu2P-o-C6H4)-CMe2]−) reacts with silver(I) acetate to yield the monomeric κ2-acetate complex [(PC)Pt(κ2-OOCMe)]. Its trifluoroacetate analogue exists in solution as a mixture of the monomer and two isomeric dimers, and crystallizes as the approximately C2-symmetrical dimer [(PC)Pt(μ-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 = (tBu2P-o-C6H4)-C(Me)=CH2).