The Role of Seven Coordination in Ru-catalyzed Water Oxidation

A family of Ru complexes based on the pentadentate t5a3- ligand ((2,5-bis(6-carboxylatopyridin-2- yl)pyrrol-1-ide) and pyridine (py) that include, {RuII(Ht5a--N2O)(py)3}, 1HII(-N2O), {RuIII(t5a-- N3O1.5)(py)2}, 2III(-N3O1.5) and {RuIV(t5a--N3O2)(py)2}+, {2IV(-N3O2)}+ has been prepared and thor...

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Autores: Matheu, Roc, Ertem, Mehmed Z, Pipelier, Muriel, Lebreton, Jacques, Dubreuil, Didier, Benet-Buchholz, Jordi, Sala, Xavier, Tessier, Arnaud, Llobet, Antoni
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/307100
Acceso en línea:http://hdl.handle.net/2072/307100
https://doi.org/10.1021/acscatal.7b03638
Access Level:acceso abierto
Palabra clave:54 - Química
54
547
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spelling The Role of Seven Coordination in Ru-catalyzed Water OxidationMatheu, RocErtem, Mehmed ZPipelier, MurielLebreton, JacquesDubreuil, DidierBenet-Buchholz, JordiSala, XavierTessier, ArnaudLlobet, Antoni54 - Química54547A family of Ru complexes based on the pentadentate t5a3- ligand ((2,5-bis(6-carboxylatopyridin-2- yl)pyrrol-1-ide) and pyridine (py) that include, {RuII(Ht5a--N2O)(py)3}, 1HII(-N2O), {RuIII(t5a-- N3O1.5)(py)2}, 2III(-N3O1.5) and {RuIV(t5a--N3O2)(py)2}+, {2IV(-N3O2)}+ has been prepared and thoroughly characterized. Complexes 1HII(-N2O), 2III(-N3O1.5) and {2IV(-N3O2)}+ have been investigated in solution by spectroscopic methods (NMR, UV-vis) and in the solid state by single- crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2III(-N3O1.5) have been studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a3- ligand. In neutral to basic conditions complex {2IV(-N3O2)}+ undergoes aquation generating {RuIV(OH)(t5a--N2O)(py)2}, 2IV(OH)(-N2O). Further oxidation of the complex forms {RuV(O)(t5a--N2O)(py)2}, 2V(O)(-N2O) that is a very efficient water oxidation catalyst, reaching TOFMAX of 9400 s-1 at pH = 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2V(O)(-N2O) is due to not only the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the non- coordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.American Chemical Society2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion23 p.application/pdfhttp://hdl.handle.net/2072/307100https://doi.org/10.1021/acscatal.7b03638RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésACS Catalysis© 2018 American Chemical Societyinfo:eu-repo/semantics/openAccessoai:recercat.cat:2072/3071002026-05-29T05:05:01Z
dc.title.none.fl_str_mv The Role of Seven Coordination in Ru-catalyzed Water Oxidation
title The Role of Seven Coordination in Ru-catalyzed Water Oxidation
spellingShingle The Role of Seven Coordination in Ru-catalyzed Water Oxidation
Matheu, Roc
54 - Química
54
547
title_short The Role of Seven Coordination in Ru-catalyzed Water Oxidation
title_full The Role of Seven Coordination in Ru-catalyzed Water Oxidation
title_fullStr The Role of Seven Coordination in Ru-catalyzed Water Oxidation
title_full_unstemmed The Role of Seven Coordination in Ru-catalyzed Water Oxidation
title_sort The Role of Seven Coordination in Ru-catalyzed Water Oxidation
dc.creator.none.fl_str_mv Matheu, Roc
Ertem, Mehmed Z
Pipelier, Muriel
Lebreton, Jacques
Dubreuil, Didier
Benet-Buchholz, Jordi
Sala, Xavier
Tessier, Arnaud
Llobet, Antoni
author Matheu, Roc
author_facet Matheu, Roc
Ertem, Mehmed Z
Pipelier, Muriel
Lebreton, Jacques
Dubreuil, Didier
Benet-Buchholz, Jordi
Sala, Xavier
Tessier, Arnaud
Llobet, Antoni
author_role author
author2 Ertem, Mehmed Z
Pipelier, Muriel
Lebreton, Jacques
Dubreuil, Didier
Benet-Buchholz, Jordi
Sala, Xavier
Tessier, Arnaud
Llobet, Antoni
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv 54 - Química
54
547
topic 54 - Química
54
547
description A family of Ru complexes based on the pentadentate t5a3- ligand ((2,5-bis(6-carboxylatopyridin-2- yl)pyrrol-1-ide) and pyridine (py) that include, {RuII(Ht5a--N2O)(py)3}, 1HII(-N2O), {RuIII(t5a-- N3O1.5)(py)2}, 2III(-N3O1.5) and {RuIV(t5a--N3O2)(py)2}+, {2IV(-N3O2)}+ has been prepared and thoroughly characterized. Complexes 1HII(-N2O), 2III(-N3O1.5) and {2IV(-N3O2)}+ have been investigated in solution by spectroscopic methods (NMR, UV-vis) and in the solid state by single- crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2III(-N3O1.5) have been studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a3- ligand. In neutral to basic conditions complex {2IV(-N3O2)}+ undergoes aquation generating {RuIV(OH)(t5a--N2O)(py)2}, 2IV(OH)(-N2O). Further oxidation of the complex forms {RuV(O)(t5a--N2O)(py)2}, 2V(O)(-N2O) that is a very efficient water oxidation catalyst, reaching TOFMAX of 9400 s-1 at pH = 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2V(O)(-N2O) is due to not only the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the non- coordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.
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 http://hdl.handle.net/2072/307100
https://doi.org/10.1021/acscatal.7b03638
url http://hdl.handle.net/2072/307100
https://doi.org/10.1021/acscatal.7b03638
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv ACS Catalysis
dc.rights.none.fl_str_mv © 2018 American Chemical Society
info:eu-repo/semantics/openAccess
rights_invalid_str_mv © 2018 American Chemical Society
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 23 p.
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 RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.81155

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