Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water

A new cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(8,9,12-Cl3-1,2-C2B9H8)2]2, 5, has been synthesized and fully characterized for the first time. In this system, the photoredox catalyst [3,3′-Co(8,9,12-Cl3-1,2-C2B9H8)2]− [Cl6-1]−, a metallacarborane, and the oxidation cata...

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Autores: Guerrero Troyano, Isabel, Viñas Teixidor, Clara, Teixidor Bombardó, Francesc, Romero García, Isabel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
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:10256/24964
Acceso en línea:http://hdl.handle.net/10256/24964
Access Level:acceso abierto
Palabra clave:Catàlisi
Catalysis
Alquens -- Oxidació
Alkenes -- Oxidation
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spelling Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in WaterGuerrero Troyano, IsabelViñas Teixidor, ClaraTeixidor Bombardó, FrancescRomero García, IsabelCatàlisiCatalysisAlquens -- OxidacióAlkenes -- OxidationA new cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(8,9,12-Cl3-1,2-C2B9H8)2]2, 5, has been synthesized and fully characterized for the first time. In this system, the photoredox catalyst [3,3′-Co(8,9,12-Cl3-1,2-C2B9H8)2]− [Cl6-1]−, a metallacarborane, and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+, 2 are linked by non-covalent interactions. This compound, along with the one previously synthesized by us, [RuII(trpy)(bpy)(H2O)][(3,3′-Co(1,2-C2B9H11)2]2, 4, are the only examples of cooperative molecular photocatalysts in which the catalyst and photosensitizer are not linked by covalent bonds. Both cooperative systems have proven to be efficient photocatalysts for the oxidation of alkenes in water through Proton Coupled Electron Transfer processes (PCETs). Using 0.05 mol% of catalyst 4, total conversion values were achieved after 15 min with moderate selectivity for the corresponding epoxides, which decreases with reaction time, along with the TON values. However, with 0.005 mol% of catalyst, the conversion values are lower, but the selectivity and TON values are higher. This occurs simultaneously with an increase in the amount of the corresponding diol for most of the substrates studied. Photocatalyst 4 acts as a photocatalyst in both the epoxidation of alkenes and their hydroxylation in aqueous medium. The hybrid system 5 shows generally higher conversion values at low loads compared to those obtained with 4 for most of the substrates studied. However, the selectivity values for the corresponding epoxides are lower even after 15 min of reaction. This is likely due to the enhanced oxidizing capacity of CoIV in catalyst 5, resulting from the presence of more electron-withdrawing substituents on the metallacarborane platformThis work was financially supported by AGAUR (Generalitat de Catalunya, project 2021-SGR-00442), MICINN (PID2019-106832RB-I00, PID2022-136892NB-I00), and the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE CEX2019-000917-S project)MDPI (Multidisciplinary Digital Publishing Institute)2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/24964Molecules, 2024, vol. 29, núm. 10, p. 2378Articles 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/10.3390/molecules29102378info:eu-repo/semantics/altIdentifier/eissn/1420-3049Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/249642026-05-29T05:05:01Z
dc.title.none.fl_str_mv Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
title Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
spellingShingle Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
Guerrero Troyano, Isabel
Catàlisi
Catalysis
Alquens -- Oxidació
Alkenes -- Oxidation
title_short Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
title_full Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
title_fullStr Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
title_full_unstemmed Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
title_sort Unveiling Non-Covalent Interactions in Novel Cooperative Photoredox Systems for Efficient Alkene Oxidation in Water
dc.creator.none.fl_str_mv Guerrero Troyano, Isabel
Viñas Teixidor, Clara
Teixidor Bombardó, Francesc
Romero García, Isabel
author Guerrero Troyano, Isabel
author_facet Guerrero Troyano, Isabel
Viñas Teixidor, Clara
Teixidor Bombardó, Francesc
Romero García, Isabel
author_role author
author2 Viñas Teixidor, Clara
Teixidor Bombardó, Francesc
Romero García, Isabel
author2_role author
author
author
dc.subject.none.fl_str_mv Catàlisi
Catalysis
Alquens -- Oxidació
Alkenes -- Oxidation
topic Catàlisi
Catalysis
Alquens -- Oxidació
Alkenes -- Oxidation
description A new cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(8,9,12-Cl3-1,2-C2B9H8)2]2, 5, has been synthesized and fully characterized for the first time. In this system, the photoredox catalyst [3,3′-Co(8,9,12-Cl3-1,2-C2B9H8)2]− [Cl6-1]−, a metallacarborane, and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+, 2 are linked by non-covalent interactions. This compound, along with the one previously synthesized by us, [RuII(trpy)(bpy)(H2O)][(3,3′-Co(1,2-C2B9H11)2]2, 4, are the only examples of cooperative molecular photocatalysts in which the catalyst and photosensitizer are not linked by covalent bonds. Both cooperative systems have proven to be efficient photocatalysts for the oxidation of alkenes in water through Proton Coupled Electron Transfer processes (PCETs). Using 0.05 mol% of catalyst 4, total conversion values were achieved after 15 min with moderate selectivity for the corresponding epoxides, which decreases with reaction time, along with the TON values. However, with 0.005 mol% of catalyst, the conversion values are lower, but the selectivity and TON values are higher. This occurs simultaneously with an increase in the amount of the corresponding diol for most of the substrates studied. Photocatalyst 4 acts as a photocatalyst in both the epoxidation of alkenes and their hydroxylation in aqueous medium. The hybrid system 5 shows generally higher conversion values at low loads compared to those obtained with 4 for most of the substrates studied. However, the selectivity values for the corresponding epoxides are lower even after 15 min of reaction. This is likely due to the enhanced oxidizing capacity of CoIV in catalyst 5, resulting from the presence of more electron-withdrawing substituents on the metallacarborane platform
publishDate 2024
dc.date.none.fl_str_mv 2024
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/10256/24964
url http://hdl.handle.net/10256/24964
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.3390/molecules29102378
info:eu-repo/semantics/altIdentifier/eissn/1420-3049
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 MDPI (Multidisciplinary Digital Publishing Institute)
publisher.none.fl_str_mv MDPI (Multidisciplinary Digital Publishing Institute)
dc.source.none.fl_str_mv Molecules, 2024, vol. 29, núm. 10, p. 2378
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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