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

Abstract

The chloro-bridged dimer [(PC)Pt(mu-Cl)](2) (PC = [((t)Bu(2)P-o-C(6)H(4))-CMe(2)](-)) 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-OOCCF(3))](2). NMR experiments and density functional theory calculations show that the monomeric species are favored by bulky ligands and electron-rich carboxylates. [(PC)Pt(OOCCF(3))] undergoes a ligand-dehydrogenation reaction in hot trifluoroacetic acid to yield [(PCC)Pt(OOCCF(3))(2)] (PCC = ((t)Bu(2)P-o-C(6)H(4))-C(Me)=CH(2)).