Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands

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 shor...

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Autor principal:	Doctorovich, Fabio Ariel
Publicado:	2017
Materias:	Dimerization Kinetics Mn catalysts SOD/CAT activity Structure antioxidant catalase dimer ligand manganese derivative monomer peroxide Schiff base superoxide superoxide dismutase water chlorinated hydrocarbon coordination compound fluorinated hydrocarbon manganese 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
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v167_n_p49_Palopoli http://hdl.handle.net/20.500.12110/paper_01620134_v167_n_p49_Palopoli
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

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spelling	paper:paper_01620134_v167_n_p49_Palopoli2023-06-08T15:13:36Z Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands Doctorovich, Fabio Ariel 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 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. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2017 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v167_n_p49_Palopoli http://hdl.handle.net/20.500.12110/paper_01620134_v167_n_p49_Palopoli
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	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
spellingShingle	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 Doctorovich, Fabio Ariel Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
topic_facet	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
description	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.
author	Doctorovich, Fabio Ariel
author_facet	Doctorovich, Fabio Ariel
author_sort	Doctorovich, Fabio Ariel
title	Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
title_short	Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
title_full	Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
title_fullStr	Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
title_full_unstemmed	Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands
title_sort	dimerization, redox properties and antioxidant activity of two manganese(iii) complexes of difluoro- and dichloro-substituted schiff-base ligands
publishDate	2017
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01620134_v167_n_p49_Palopoli http://hdl.handle.net/20.500.12110/paper_01620134_v167_n_p49_Palopoli
work_keys_str_mv	AT doctorovichfabioariel dimerizationredoxpropertiesandantioxidantactivityoftwomanganeseiiicomplexesofdifluoroanddichlorosubstitutedschiffbaseligands
_version_	1768546623570313216

Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands

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