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dc.contributor.author
Palopoli, Claudia Marcela
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dc.contributor.author
Duhayon, Carine
dc.contributor.author
Tuchagues, Jean Pierre
dc.contributor.author
Signorella, Sandra Rosanna
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dc.date.available
2016-06-03T21:38:35Z
dc.date.issued
2014-09
dc.identifier.citation
Palopoli, Claudia Marcela; Duhayon, Carine; Tuchagues, Jean Pierre; Signorella, Sandra Rosanna; Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase; Royal Society of Chemistry; Dalton Transactions; 43; 45; 9-2014; 17145-17155
dc.identifier.issn
0300-9246
dc.identifier.uri
http://hdl.handle.net/11336/6048
dc.description.abstract
A new diMnIII complex, Na[Mn2(5-SO3-salpentO)(μ-OAc)(μ-OMe)(H2O)]·4H2O, where 5-SO3-salpentOH = 1,5-bis(5-sulphonatosalicylidenamino)pentan-3-ol, has been prepared and characterized. ESI-mass spectrometry, paramagnetic 1H NMR, EPR and UV-visible spectroscopic studies on freshly prepared solutions of the complex in methanol and 9 : 1 methanol–water mixtures showed that the compound retains the triply bridged bis(μ-alkoxo)(μ-acetato)Mn23+ core in solution. In the 9 : 1 methanol–water mixture, slow substitution of acetate by water molecules took place, and after one month, the doubly bridged diMnIII complex, [Mn2(5-SO3-salpentO)(μ-OMe)(H2O)3]·5H2O, formed and could be characterized by X-ray diffraction analysis. In methanolic or aqueous basic media, acetate shifts from a bridging to a terminal coordination mode, affording the highly stable [Mn2(5-SO3-salpentO)(μ-OMe)(OAc)]− anion. The efficiency of the complex in disproportionating H2O2 depends on the solvent and correlates with the stability of the complex (towards metal dissociation) in each medium: basic buffer > aqueous base > water. The buffer preserves the integrity of the catalyst and the rate of O2 evolution remains essentially constant after successive additions of excess of H2O2. Turnovers as high as 3000 mol H2O2 per mol of catalyst, without significant decomposition and with an efficiency of kcat/KM = 1028 M−1 s−1, were measured for the complex in aqueous buffers of pH 11. Kinetic and spectroscopic results suggest a catalytic cycle that runs between MnIII2 and MnIV2 oxidation states, which is consistent with the low redox potential observed for the MnIII2/MnIIIMnIV couple of the catalyst in basic medium.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Mn Catalyst
dc.subject
Catalase Activity
dc.subject
Structure
dc.subject
Kinetics
dc.subject.classification
Química Inorgánica y Nuclear
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
Synthesis, characterization, and reactivity studies of a water-soluble bis(alkoxo)(carboxylato)- bridged diMnIII complex modeling the active site in catalase
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2016-06-01T14:04:12Z
dc.journal.volume
43
dc.journal.number
45
dc.journal.pagination
17145-17155
dc.journal.pais
Reino Unido
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dc.journal.ciudad
Cambridge
dc.description.fil
Fil: Palopoli, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
dc.description.fil
Fil: Duhayon, Carine. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; Francia
dc.description.fil
Fil: Tuchagues, Jean Pierre. Universite de Toulose - Le Mirail; Francia. Laboratoire de Chimie de Coordination; Francia
dc.description.fil
Fil: Signorella, Sandra Rosanna. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina
dc.journal.title
Dalton Transactions
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2014/DT/C4DT01907E
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1039/C4DT01907E
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