A New Mixed-Valence Mn(II)Mn(III) Compound With Catalase and Superoxide Dismutase Activities

The synthesis, X-ray molecular structure, physico-chemical characterization and dual antioxidant activity (catalase and superoxide dismutase) of a new polymeric mixed valence Mn(III)Mn(II) complex, containing the ligand H2BPCINOL (N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)[(3-chloro)(2-hydroxy)] propylamine) is described. The monomeric unit is composed of a dinuclear Mn(II)Mn(III) moiety, [Mn(III)(mu-HBPCINOL)(mu-BPCINOL)Mn(II)(Cl)](ClO4)center dot 2H(2)O, 1, in which the Mn ions are connected by two different bridging groups provided by two molecules of the ligand H2BPCINOL, a phenoxide and an alkoxide group. In the solid state, this mixed valence dinuclear unit is connected to its neighbors through chloro bridges. Magnetic measurements indicated the presence of ferromagnetic [J = +0.076(13) cm(-1)] and antiferromagnetic [J = -5.224(13) cm(-1)] interactions. The compound promotes O-2(center dot-) dismutation in aqueous solution (IC50 = 0.370 mu mol dm(-3), k(cat) = 3.6x10(6) M-1 s(-1)). EPR studies revealed that a high-valent Mn(III)-O-Mn(IV) species is involved in the superoxide dismutation catalytic cycle. Complex 1 shows catalase activity only in the presence of a base, e.g., piperazine or triethylamine. Kinetic studies were carried out in the presence of piperazine and employing two different methods, resulting in k cat values of 0.58 +/- 0.03 s(-1) (detection of O-2 production employing a Clark electrode) and 2.59 +/- 0.12 s(-1) (H2O2 consuption recorded via UV-Vis). EPR and ESI-(+)-MS studies indicate that piperazine induces the oxidation of 1, resulting in the formation of the catalytically active Mn(III)-O-Mn(IV) species.