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Abstract:

Two mononuclear MnIII complexes [Mn(3,5-F2salpn)(H2O)2][B(C6H5)4]·2H2O (1·2H2O) and [Mn(3,5-Cl2salpn)(OAc)(H2O)]·H2O (2·H2O), where H2salpn = 1,3-bis(salicylidenamino)propane, have been prepared and characterized. The crystal structure of 1·H2O shows that this complex forms μ-aqua dimers with a short Mn ⋯ Mn distance of 4.93 Å. Under anaerobic conditions, the two complexes are stable in solution and possess trans-diaxial symmetry with the tetradentate Schiff base ligand symmetrically arranged in the equatorial plane. When left in air, these complexes slowly dimerize to yield high-valent [MnIV2(3,5-X2-salpn)2(μ-O)2] in which each X2-salpn ligand wraps the two Mn ions. This process is favored in basic medium where the deprotonation of the bound water molecule is concomitant with air oxidation. The two complexes catalyze the dismutation of superoxide (superoxide dismutase (SOD) activity) and peroxide (catalase (CAT) activity) in basic medium. The phenyl-ring substituents play an important role on the CAT reaction but have little effect on SOD activity. Kinetics and spectroscopic results indicate that 1 and 2 catalyze H2O2 disproportionation through a cycle involving MnIII2 and MnIV2 dimers, unlike related complexes with a more rigid and smaller chelate ring, which employ MnIII/MnV[dbnd]O monomers. © 2016 Elsevier Inc.

Registro:

Documento: Artículo
Título:Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
Autor:Palopoli, C.; Gómez, G.; Foi, A.; Doctorovich, F.; Mallet-Ladeira, S.; Hureau, C.; Signorella, S.
Filiación:IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario, S2002LRK, Argentina
Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires, C1428EHA, Argentina
Institut de Chimie de Toulouse, FR 2599, 118 Route de Narbonne, Toulouse, F-31062, France
CNRS, LCC (Laboratoire de Chimie de Coordination) and UPS, INPT, LCC, Université de Toulouse, 205 route de Narbonne, Toulouse, F-31077, France
Palabras clave:Dimerization; Kinetics; Mn catalysts; SOD/CAT activity; Structure; antioxidant; catalase; dimer; ligand; manganese derivative; monomer; peroxide; Schiff base; superoxide; superoxide dismutase; water; antioxidant; chlorinated hydrocarbon; coordination compound; fluorinated hydrocarbon; manganese; Schiff base; antioxidant activity; Article; catalysis; crystal structure; deprotonation; dimerization; drug structure; drug synthesis; electrospray mass spectrometry; enzyme activity; fluorine nuclear magnetic resonance; infrared spectroscopy; oxidation reduction potential; proton nuclear magnetic resonance; proton transport; X ray diffraction; Antioxidants; Catalase; Coordination Complexes; Hydrocarbons, Chlorinated; Hydrocarbons, Fluorinated; Manganese; Schiff Bases; Superoxide Dismutase
Año:2017
Volumen:167
Página de inicio:49
Página de fin:59
DOI: http://dx.doi.org/10.1016/j.jinorgbio.2016.11.019
Título revista:Journal of Inorganic Biochemistry
Título revista abreviado:J. Inorg. Biochem.
ISSN:01620134
CODEN:JIBID
CAS:catalase, 9001-05-2; peroxide, 14915-07-2; superoxide, 11062-77-4; superoxide dismutase, 37294-21-6, 9016-01-7, 9054-89-1; water, 7732-18-5; manganese, 16397-91-4, 7439-96-5; Antioxidants; Catalase; Coordination Complexes; Hydrocarbons, Chlorinated; Hydrocarbons, Fluorinated; Manganese; Schiff Bases; Superoxide Dismutase
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v167_n_p49_Palopoli

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Citas:

---------- APA ----------
Palopoli, C., Gómez, G., Foi, A., Doctorovich, F., Mallet-Ladeira, S., Hureau, C. & Signorella, S. (2017) . Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands. Journal of Inorganic Biochemistry, 167, 49-59.
http://dx.doi.org/10.1016/j.jinorgbio.2016.11.019
---------- CHICAGO ----------
Palopoli, C., Gómez, G., Foi, A., Doctorovich, F., Mallet-Ladeira, S., Hureau, C., et al. "Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands" . Journal of Inorganic Biochemistry 167 (2017) : 49-59.
http://dx.doi.org/10.1016/j.jinorgbio.2016.11.019
---------- MLA ----------
Palopoli, C., Gómez, G., Foi, A., Doctorovich, F., Mallet-Ladeira, S., Hureau, C., et al. "Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands" . Journal of Inorganic Biochemistry, vol. 167, 2017, pp. 49-59.
http://dx.doi.org/10.1016/j.jinorgbio.2016.11.019
---------- VANCOUVER ----------
Palopoli, C., Gómez, G., Foi, A., Doctorovich, F., Mallet-Ladeira, S., Hureau, C., et al. Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands. J. Inorg. Biochem. 2017;167:49-59.
http://dx.doi.org/10.1016/j.jinorgbio.2016.11.019