Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square
A kineticomechanistic study of reversible electron-transfer processes undergone by the water-soluble, cyanido-bridged mixed-valence [{CoIII{(Me)2(μ-ET)cyclen}}2{(μ-NC)2FeII(CN)4}2]2- square has been carried out. The oxidation reaction consists of a two-step process with the participation of a solven...
| Autores: | , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2018 |
| País: | España |
| Institución: | Universidad de Barcelona |
| Repositorio: | Dipòsit Digital de la UB |
| OAI Identifier: | oai:diposit.ub.edu:2445/142958 |
| Acceso en línea: | https://hdl.handle.net/2445/142958 |
| Access Level: | acceso abierto |
| Palabra clave: | Complexos metàl·lics Propietats magnètiques Lligands Metal complexes Magnetic properties Ligands |
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Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 squareAlcázar, LauraBernhardt, Paul V.Ferrer García, MontserratFont Bardia, Ma. MercedesGallen Ortiz, AlbertJover Modrego, JesúsMartínez López, Manuel, 1957-Peters, JackZerk, Timothy J.Complexos metàl·licsPropietats magnètiquesLligandsMetal complexesMagnetic propertiesLigandsA kineticomechanistic study of reversible electron-transfer processes undergone by the water-soluble, cyanido-bridged mixed-valence [{CoIII{(Me)2(μ-ET)cyclen}}2{(μ-NC)2FeII(CN)4}2]2- square has been carried out. The oxidation reaction consists of a two-step process with the participation of a solvent-assisted outer-sphere complex, as a result of the establishment of hydrogen bonds that involve the oxo groups of the oxidant (peroxodisulfate) and the terminal cyanido ligands of the tetrametallic square. The formally endergonic reduction reaction of the fully oxidized ([{CoIII{(Me)2(μ-ET)cyclen}}2{(μ-NC)2FeIII(CN)4}2]) core by water, producing hydrogen peroxide from water even at low pH values, is also a two-step process. Each one of these processes requires a set of two preequilibria involving the association of OH- and its subsequent deprotonation by a further OH- anion. The structure of the square compound in its fully protonated form has also been determined by X-ray diffraction and shows the existence of strong hydrogen-bonding interactions, in agreement with the rather high basicity of the terminal cyanido ligands. Likewise, density functional theory calculations on the tetrametallic complex showed zones with negative electrostatic potential around the FeII centers of the square that would account for the establishment of the hydrogen bonds found in the solid state. Spectroelectrochemistry experiments demonstrated the singular stability of the {CoIII/FeII}2 2- complex, as well as that of their partially, {Co2 III/FeIIIFeII}-, and fully, {CoIII/FeIII}2, oxidized counterparts because no hysteresis was observed in these measurements..American Chemical Society2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/142958Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.8b01147Inorganic Chemistry, 2018, vol. 57, num. 14, p. 8465-8475https://doi.org/10.1021/acs.inorgchem.8b01147(c) American Chemical Society , 2018info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1429582026-05-27T06:46:51Z |
| dc.title.none.fl_str_mv |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| title |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| spellingShingle |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square Alcázar, Laura Complexos metàl·lics Propietats magnètiques Lligands Metal complexes Magnetic properties Ligands |
| title_short |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| title_full |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| title_fullStr |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| title_full_unstemmed |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| title_sort |
Kineticomechanistic study of the redox pH cycling processes occurring on a robust water-soluble cyanido-bridged mixed-valence {CoIII/FeII}2 square |
| dc.creator.none.fl_str_mv |
Alcázar, Laura Bernhardt, Paul V. Ferrer García, Montserrat Font Bardia, Ma. Mercedes Gallen Ortiz, Albert Jover Modrego, Jesús Martínez López, Manuel, 1957- Peters, Jack Zerk, Timothy J. |
| author |
Alcázar, Laura |
| author_facet |
Alcázar, Laura Bernhardt, Paul V. Ferrer García, Montserrat Font Bardia, Ma. Mercedes Gallen Ortiz, Albert Jover Modrego, Jesús Martínez López, Manuel, 1957- Peters, Jack Zerk, Timothy J. |
| author_role |
author |
| author2 |
Bernhardt, Paul V. Ferrer García, Montserrat Font Bardia, Ma. Mercedes Gallen Ortiz, Albert Jover Modrego, Jesús Martínez López, Manuel, 1957- Peters, Jack Zerk, Timothy J. |
| author2_role |
author author author author author author author author |
| dc.subject.none.fl_str_mv |
Complexos metàl·lics Propietats magnètiques Lligands Metal complexes Magnetic properties Ligands |
| topic |
Complexos metàl·lics Propietats magnètiques Lligands Metal complexes Magnetic properties Ligands |
| description |
A kineticomechanistic study of reversible electron-transfer processes undergone by the water-soluble, cyanido-bridged mixed-valence [{CoIII{(Me)2(μ-ET)cyclen}}2{(μ-NC)2FeII(CN)4}2]2- square has been carried out. The oxidation reaction consists of a two-step process with the participation of a solvent-assisted outer-sphere complex, as a result of the establishment of hydrogen bonds that involve the oxo groups of the oxidant (peroxodisulfate) and the terminal cyanido ligands of the tetrametallic square. The formally endergonic reduction reaction of the fully oxidized ([{CoIII{(Me)2(μ-ET)cyclen}}2{(μ-NC)2FeIII(CN)4}2]) core by water, producing hydrogen peroxide from water even at low pH values, is also a two-step process. Each one of these processes requires a set of two preequilibria involving the association of OH- and its subsequent deprotonation by a further OH- anion. The structure of the square compound in its fully protonated form has also been determined by X-ray diffraction and shows the existence of strong hydrogen-bonding interactions, in agreement with the rather high basicity of the terminal cyanido ligands. Likewise, density functional theory calculations on the tetrametallic complex showed zones with negative electrostatic potential around the FeII centers of the square that would account for the establishment of the hydrogen bonds found in the solid state. Spectroelectrochemistry experiments demonstrated the singular stability of the {CoIII/FeII}2 2- complex, as well as that of their partially, {Co2 III/FeIIIFeII}-, and fully, {CoIII/FeIII}2, oxidized counterparts because no hysteresis was observed in these measurements.. |
| publishDate |
2018 |
| dc.date.none.fl_str_mv |
2018 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion |
| format |
article |
| status_str |
acceptedVersion |
| dc.identifier.none.fl_str_mv |
https://hdl.handle.net/2445/142958 |
| url |
https://hdl.handle.net/2445/142958 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
Versió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.8b01147 Inorganic Chemistry, 2018, vol. 57, num. 14, p. 8465-8475 https://doi.org/10.1021/acs.inorgchem.8b01147 |
| dc.rights.none.fl_str_mv |
(c) American Chemical Society , 2018 info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
(c) American Chemical Society , 2018 |
| eu_rights_str_mv |
openAccess |
| dc.format.none.fl_str_mv |
application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| publisher.none.fl_str_mv |
American Chemical Society |
| dc.source.none.fl_str_mv |
Articles publicats en revistes (Química Inorgànica i Orgànica) reponame:Dipòsit Digital de la UB instname:Universidad de Barcelona |
| instname_str |
Universidad de Barcelona |
| reponame_str |
Dipòsit Digital de la UB |
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Dipòsit Digital de la UB |
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1869410104839766016 |
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15,300724 |