title: Synthesis, characterization, and catalase activity of a water-soluble diMn(III) complex of a sulphonato-substituted Schiff base ligand: an efficient catalyst for H2O2 disproportionation.
abstract: A new diMn(III) complex, Na[Mn(2)(3-Me-5-SO(3)-salpentO)(μ-MeO)(μ-AcO)(H(2)O)]·4H(2)O (1), where salpentOH = 1,5-bis(salicylidenamino) pentan-3-ol, was synthesized and structurally characterized. The complex possesses a bis(μ-alkoxo)(μ-acetato) triply bridged diMn(III) core, the structure of which is retained upon dissolution. Complex 1 is highly efficient to disproportionate H(2)O(2) in an aqueous solution of pH ≥ 8.5 or in DMF, with only a slight decrease of activity. Electrospray ionization mass spectrometry, EPR, and UV-vis spectroscopy used to monitor the H(2)O(2) disproportionation in buffered basic medium, suggest that the major active form of the catalyst during cycling occurs in the Mn(III)(2) oxidation state and that the starting complex retains the dinuclearity and composition during catalysis, with the acetate that moves from bridging to terminal ligand. UV-vis and Raman spectroscopy of H(2)O(2) + 1 + Bu(4)NOH mixtures in DMF suggest that the catalytic cycle involves Mn(III)(2)/Mn(IV)(2) oxidation levels. At pH 10.6 in an Et(3)N/Et(3)NH(+) buffer, complex 1 catalyzes dismutation of H(2)O(2) with saturation kinetics on the substrate, first order dependence on the catalyst, and k(cat)/K(M) = 16(1) × 10(2) s(-1) M(-1). During catalysis, the exogenous base contributes to retain the integrity of the bis(μ-alkoxo) doubly bridged diMn core and favors the formation of the catalyst-peroxide adduct (low value of K(M)), rendering 1 a highly efficient catalyst for H(2)O(2) disproportionation.
authors.affiliation: Departamento de Química Física/IQUIR-CONICET, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina.
authors.forename: Claudia
authors.initials: C
authors.lastname: Palopoli
authors.forename: Natalia
authors.initials: N
authors.lastname: Bruzzo
authors.forename: Christelle
authors.initials: C
authors.lastname: Hureau
authors.forename: Sonia
authors.initials: S
authors.lastname: Ladeira
authors.forename: Daniel
authors.initials: D
authors.lastname: Murgida
authors.forename: Sandra
authors.initials: S
authors.lastname: Signorella
mesh_terms: D002374:Catalase / Q000378:metabolism*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry / Q000378:metabolism*; D006861:Hydrogen Peroxide / Q000378:metabolism*; D008024:Ligands; D008345:Manganese / Q000737:chemistry / Q000378:metabolism*; D008958:Models, Molecular; D012545:Schiff Bases / Q000737:chemistry / Q000378:metabolism*; D013057:Spectrum Analysis
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D012545:Schiff Bases; D008345:Manganese; D006861:Hydrogen Peroxide; D002374:Catalase