Hydrogen peroxide as oxidant in bio-mimetic catalysis by manganese porphyrin: Theoretical DFT studies

Abstract

The aim of this study is to elucidate the geometry and electronic structure of various adducts that may be formed between manganese(III) (Mn(III)) porphyrin and hydrogen peroxide. Hydrogen peroxide may interact with Mn(III) porphyrin either as H2O2 or, after dissociation, as OOH–. In the former, it may decompose into two hydroxo groups, which acquire OH– character or an oxo group (=O) and a water molecule. Therefore, the following systems are considered: MnP(H2O2)+, MnP(H2O2)(OH), MnP(OH)3, [Formula: see text], MnPO+, MnPO(OH), MnP(OOH), MnP(OOH)(OH)–, and the possible transformations between them are taken into account. The reported studies are performed within the Density Functional Theory (DFT) method with the GGA-BP functional. The geometry and electronic structures of the structures found along the studied reaction pathways are discussed in terms of interatomic distances, valence angles, Mulliken charges, and spin densities. It was found that different active oxygen species may be formed in the reaction between Mn(III) porphyrin and hydrogen peroxide. As manganese is a transition metal, numerous possible spin states for each of the studied structures are found, where the relative energies of different multiplicities depend strongly on the ligands present in the complex. In view of the catalytic properties, all oxygen-containing ligands are negatively charged, which results in their behaviour as nucleophiles towards hydrocarbons. Finally, the analysis of charge and spin populations on different parts of the studied systems indicate the porphyrin ligand as active in charge transfer processes.