THEORETICAL-STUDY OF THE REACTIVITY OF (PPH3)2PT(ETA-2-O2) WITH ACIDS

Ab initio Hartree Fock (HF) calculations have been carried out on a se ries of complexes which model (PPh3)2Pt(eta2O2) and its derivatives ob tained by reaction with hydrochloric, formic and oxalic acid. All the structures of the complexes have been obtained from full HF geometry o ptimization; the HF energies have been corrected for correlation effec ts using a density functional approach. The first reaction step corres ponds to the protonation of the eta2-coordinated dioxygen with formati on of a hydroperoxide intermediate. The second reaction gives H2O2. Th e trend in the computed reaction energies is discussed in terms of the coordinating ability of the anionic group of the considered acid.