Greco, R.; Tiburcio-Fortes, E.; Fernandez, A.; Marini, C.; Vidal Moya, JA.; Oliver-Meseguer, J.; Armentano, D.... (2022). MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids. Chemistry - A European Journal. 28(7). https://doi.org/10.1002/chem.202103781
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/208622
Título:
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MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids
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Autor:
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Greco, Rossella
Tiburcio-Fortes, Estefania
Fernandez, Antonio
Marini, Carlo
Vidal Moya, José Alejandro
Oliver-Meseguer, Judit
Armentano, Donatella
Pardo, Emilio
Ferrando-Soria, Jesus
Leyva Perez, Antonio
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Entidad UPV:
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Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química
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Fecha difusión:
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Resumen:
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[EN] Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor sigma-donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. ...[+]
[EN] Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor sigma-donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. However, their low lifetime prevents any use in catalysis. Here we show the synthesis of fluorinated pyridine-Pd2+ coordinate cages within the channels of an anionic tridimensional metal-organic framework (MOF), and their use as efficient metal catalysts for the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. Mechanistic studies strongly support that the MOF-stabilized coordination cage with perfluorinated ligands unleashes the full electrophilic potential of Pd2+ to dehydrogenate primary alcohols, without any base, and also to activate O-2 for the radical oxidation to the aldehyde intermediate. This study opens the door to design catalytic perfluorinated complexes for challenging organic transformations, where an extremely high electrophilic metal site is required.
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Palabras clave:
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Aerobic alcohol oxidation to carboxylic acid
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Metal-organic frameworks
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Per-fluorinated palladium complexes
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Single-crystal X-Ray diffraction
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Supramolecular coordination cages
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Derechos de uso:
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Cerrado |
Fuente:
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Chemistry - A European Journal. (issn:
0947-6539
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DOI:
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10.1002/chem.202103781
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Editorial:
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John Wiley & Sons
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Versión del editor:
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https://doi.org/10.1002/chem.202103781
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Código del Proyecto:
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-86735-P/ES/CATALISIS CON ATOMOS METALICOS AISLADOS Y CLUSTERES ULTRAPEQUEÑOS BIEN DEFINIDOS, SIN LIGANDOS Y CONFINADOS/
...[+]
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-86735-P/ES/CATALISIS CON ATOMOS METALICOS AISLADOS Y CLUSTERES ULTRAPEQUEÑOS BIEN DEFINIDOS, SIN LIGANDOS Y CONFINADOS/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104778GB-I00/ES/DESARROLLO DE POLIMEROS DE COORDINACION POROSOS FUNCIONALES CON APLICACIONES TECNOLOGICAS Y MEDIOAMBIENTALES/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115100GB-I00/ES/CLUSTERES CATALITICOS MULTIMETALICOS Y DE ALTA ENTROPIA PARA SINTESIS ORGANICA/
info:eu-repo/grantAgreement/EC/H2020/814804/EU/Metal-Organic Frameworks as Chemical Reactors for the Synthesis of Well-Defined Sub-Nanometer Metal Clusters/
info:eu-repo/grantAgreement/GVA//PROMETEO%2F2021%2F054/
info:eu-repo/grantAgreement/GVA//SEJI%2F2020%2F034/
info:eu-repo/grantAgreement/MCIU//SEV-2016-0683/
info:eu-repo/grantAgreement/MINECO//IJC2018-036514-I/
info:eu-repo/grantAgreement/Fundació Bancària Caixa d'Estalvis i Pensions de Barcelona//LCF%2FBQ%2FPR19%2F11700011/
info:eu-repo/grantAgreement/Fondazione Cariplo//2019-2090/
info:eu-repo/grantAgreement/MICINN//CEX2019-000919-M/
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Agradecimientos:
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This work was supported by the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy), the MICINN (Spain) (Projects PID2019-104778GB-I00, 2017-86735-P, PID2020-115100GB-I00, and Excellence Units "Severo Ochoa" ...[+]
This work was supported by the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy), the MICINN (Spain) (Projects PID2019-104778GB-I00, 2017-86735-P, PID2020-115100GB-I00, and Excellence Units "Severo Ochoa" and "Maria de Maeztu" SEV-2016-0683 and CEX2019-000919-M) and the Engineering and Physical Sciences Research Council (UK). The work has also been funded by Generalitat Valenciana, Prometeo Grupos de Investigacion de Excelencia (PROMETEU/2021/054). R.G. thanks ITQ for a contract. J.O.-M. acknowledges the Juan de la Cierva program for the concession of a contract (IJC2018-036514-I). D.A. acknowledges the financial support of the Fondazione CARIPLO/"Economia Circolare: ricerca per un futuro sostenibile" 2019, Project code: 2019-2090, MOCA and Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities and thank Dr David Allan and Sarah Barnett for their assistance at I19 beamline (Proposal No. CY22411-1). Thanks are also extended to the 2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011), the "Generalitat Valenciana" (SEJI/2020/034) and the "Ramon y Cajal" program (J.F.-S.). E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF-reactors. E. T-F thanks the MICINN for a PhD FPI grant.
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Tipo:
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Artículo
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