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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todo:paper_01620134_v167_n_p49_Palopoli2023-10-03T15:01:29Z Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands Palopoli, C. Gómez, G. Foi, A. Doctorovich, F. Mallet-Ladeira, S. Hureau, C. Signorella, S. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_01620134_v167_n_p49_Palopoli |
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Universidad de Buenos Aires |
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I-28 |
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R-134 |
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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 Palopoli, C. Gómez, G. Foi, A. Doctorovich, F. Mallet-Ladeira, S. Hureau, C. Signorella, S. 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. |
| format |
JOUR |
| author |
Palopoli, C. Gómez, G. Foi, A. Doctorovich, F. Mallet-Ladeira, S. Hureau, C. Signorella, S. |
| author_facet |
Palopoli, C. Gómez, G. Foi, A. Doctorovich, F. Mallet-Ladeira, S. Hureau, C. Signorella, S. |
| author_sort |
Palopoli, C. |
| 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 |
| url |
http://hdl.handle.net/20.500.12110/paper_01620134_v167_n_p49_Palopoli |
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