Theoretical study of the reactivity of (PPh 3) 2Pt(η 2-O 2) with acids

Abstract

Ab initio Hartree Fock (HF) calculations have been carried out on a series of complexes which model (PPh 3) 2Pt(η 2O 2) and its derivatives obtained by reaction with hydrochloric, formic and oxalic acid. All the structures of the complexes have been obtained from full HF geometry optimization; the HF energies have been corrected for correlation effects using a density functional approach. The first reaction step corresponds to the protonation of the η 2-coordinated dioxygen with formation of a hydroperoxide intermediate. The second reaction gives H 2O 2. The trend in the computed reaction energies is discussed in terms of the coordinating ability of the anionic group of the considered acid.