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

Abstract

The chloro-bridged dimer [(PC)Pt(μ-Cl)]₂ (PC = [(^tBu₂P-<i>o</i>-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 <i>C</i>₂-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-<i>o</i>-C₆H₄)-C(Me)=CH₂).