Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst

An original cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(1,2-C2B9H11)2]2 (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3′-Co(1,2-C2B9H11)2]− ([1]−) and the oxidation catalyst [RuII(trpy)(bpy...

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Autores: Guerrero Troyano, Isabel, Viñas Teixidor, Clara, Fontrodona, Xavier, Romero García, Isabel, Teixidor Bombardó, Francesc
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Recursos: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:10256/20457
Acesso em linha:http://hdl.handle.net/10256/20457
Access Level:acceso abierto
Palavra-chave:Química inorgànica
Chemistry, Inorganic
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spelling Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation CatalystGuerrero Troyano, IsabelViñas Teixidor, ClaraFontrodona, XavierRomero García, IsabelTeixidor Bombardó, FrancescQuímica inorgànicaChemistry, InorganicAn original cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(1,2-C2B9H11)2]2 (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3′-Co(1,2-C2B9H11)2]− ([1]−) and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+ (C2′) are linked by noncovalent interactions and not through covalent bonds. The noncovalent interactions to a large degree persist even after water dissolution. This represents a step ahead in cooperativity avoiding costly covalent bonding. Recrystallization of C4 in acetonitrile leads to the substitution of water by the acetonitrile ligand and the formation of complex [RuII(trpy)(bpy)(CH3CN)][3,3′-Co(1,2-C2B9H11)2]2 (C5), structurally characterized. A significant electronic coupling between C2′ and [1]− was first sensed in electrochemical studies in water. The CoIV/III redox couple in water differed by 170 mV when [1]− had Na+ as a cation versus when the ruthenium complex was the cation. This cooperative system leads to an efficient catalyst for the photooxidation of alcohols in water, through a proton-coupled electron-transfer process. We have highlighted the capacity of C4 to perform as an excellent cooperative photoredox catalyst in the photooxidation of alcohols in water at room temperature under UV irradiation, using 0.005 mol % catalyst. A high turnover number (TON = 20000) has been observed. The hybrid system C4 displays a better catalytic performance than the separated mixtures of C2′ and Na[1], with the same concentrations and ratios of Ru/Co, proving the history relevance of the photocatalyst. Cooperative systems with this type of interaction have not been described and represent a step forward in getting cooperativity avoiding costly covalent bonding. A possible mechanism has been proposedThis research has been financed by MINECO (Grants PID2019-106832RB-I00 and CTQ2015-66143-P) and Generalitat de Catalunya (Grant 2017 SGR 1720). The “Severo Ochoa” Program for Centers of Excellence in R&D 234 (SEV2015-0496) is appreciatedAmerican Chemical Society (ACS)Ministerio de Economía y Competitividad (Espanya)2021info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/20457Inorganic Chemistry, 2021, vol. 60, núm. 12, p. 8898-8907Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.1c00751info:eu-repo/semantics/altIdentifier/issn/0020-1669info:eu-repo/semantics/altIdentifier/eissn/1520-510XCTQ2015-66143-Pinfo:eu-repo/grantAgreement/MINECO//CTQ2015-66143-PAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/204572026-05-29T05:05:01Z
dc.title.none.fl_str_mv Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
title Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
spellingShingle Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
Guerrero Troyano, Isabel
Química inorgànica
Chemistry, Inorganic
title_short Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
title_full Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
title_fullStr Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
title_full_unstemmed Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
title_sort Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
dc.creator.none.fl_str_mv Guerrero Troyano, Isabel
Viñas Teixidor, Clara
Fontrodona, Xavier
Romero García, Isabel
Teixidor Bombardó, Francesc
author Guerrero Troyano, Isabel
author_facet Guerrero Troyano, Isabel
Viñas Teixidor, Clara
Fontrodona, Xavier
Romero García, Isabel
Teixidor Bombardó, Francesc
author_role author
author2 Viñas Teixidor, Clara
Fontrodona, Xavier
Romero García, Isabel
Teixidor Bombardó, Francesc
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Economía y Competitividad (Espanya)
dc.subject.none.fl_str_mv Química inorgànica
Chemistry, Inorganic
topic Química inorgànica
Chemistry, Inorganic
description An original cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(1,2-C2B9H11)2]2 (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3′-Co(1,2-C2B9H11)2]− ([1]−) and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+ (C2′) are linked by noncovalent interactions and not through covalent bonds. The noncovalent interactions to a large degree persist even after water dissolution. This represents a step ahead in cooperativity avoiding costly covalent bonding. Recrystallization of C4 in acetonitrile leads to the substitution of water by the acetonitrile ligand and the formation of complex [RuII(trpy)(bpy)(CH3CN)][3,3′-Co(1,2-C2B9H11)2]2 (C5), structurally characterized. A significant electronic coupling between C2′ and [1]− was first sensed in electrochemical studies in water. The CoIV/III redox couple in water differed by 170 mV when [1]− had Na+ as a cation versus when the ruthenium complex was the cation. This cooperative system leads to an efficient catalyst for the photooxidation of alcohols in water, through a proton-coupled electron-transfer process. We have highlighted the capacity of C4 to perform as an excellent cooperative photoredox catalyst in the photooxidation of alcohols in water at room temperature under UV irradiation, using 0.005 mol % catalyst. A high turnover number (TON = 20000) has been observed. The hybrid system C4 displays a better catalytic performance than the separated mixtures of C2′ and Na[1], with the same concentrations and ratios of Ru/Co, proving the history relevance of the photocatalyst. Cooperative systems with this type of interaction have not been described and represent a step forward in getting cooperativity avoiding costly covalent bonding. A possible mechanism has been proposed
publishDate 2021
dc.date.none.fl_str_mv 2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/20457
url http://hdl.handle.net/10256/20457
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.1c00751
info:eu-repo/semantics/altIdentifier/issn/0020-1669
info:eu-repo/semantics/altIdentifier/eissn/1520-510X
CTQ2015-66143-P
info:eu-repo/grantAgreement/MINECO//CTQ2015-66143-P
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Inorganic Chemistry, 2021, vol. 60, núm. 12, p. 8898-8907
Articles publicats (D-Q)
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 15,812429

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