A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst

The mechanism and the reactive species involved in the oxidation of alkenes, and alcohols with H2O2, catalysed by an in situ prepared mixture of a MnII salt, pyridine-2-carboxylic acid and a ketone is elucidated using substrate competition experiments, kinetic isotope effect (KIE) measurements, and...

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Detalles Bibliográficos
Autores: Kasper, Johann B., Saisaha, Pattama, Roo, Maurits de, Groen, Mitchell J., Vicens Serra, Laia, Borrell Recasens, Margarida, Boer, Johannes W. de, Hage, Ronald, Costas Salgueiro, Miquel, Browne, Wesley R.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
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:10256/23584
Acceso en línea:http://hdl.handle.net/10256/23584
Access Level:acceso abierto
Palabra clave:Oxidació
Oxidation
Alquens
Alkenes
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spelling A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato CatalystKasper, Johann B.Saisaha, PattamaRoo, Maurits deGroen, Mitchell J.Vicens Serra, LaiaBorrell Recasens, MargaridaBoer, Johannes W. deHage, RonaldCostas Salgueiro, MiquelBrowne, Wesley R.OxidacióOxidationAlquensAlkenesThe mechanism and the reactive species involved in the oxidation of alkenes, and alcohols with H2O2, catalysed by an in situ prepared mixture of a MnII salt, pyridine-2-carboxylic acid and a ketone is elucidated using substrate competition experiments, kinetic isotope effect (KIE) measurements, and atom tracking with 18O labelling. The data indicate that a single reactive species engages in the oxidation of both alkenes and alcohols. The primary KIE in the oxidation of benzyl alcohols is ca. 3.5 and shows the reactive species to be selective despite a zero order dependence on substrate concentration, and the high turnover frequencies (up to 30 s−1) observed. Selective 18O labelling identifies the origin of the oxygen atoms transferred to the substrate during oxidation, and is consistent with a highly reactive, e. g., [MnV(O)(OH)] or [MnV(O)2], species rather than an alkylperoxy or hydroperoxy speciesWiley2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewedapplication/pdfhttp://hdl.handle.net/10256/23584http://hdl.handle.net/10256/23584ChemCatChem, 2023, vol. 15, núm. 1, p. e202201072Articles 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/10.1002/cctc.202201072info:eu-repo/semantics/altIdentifier/issn/1867-3880info:eu-repo/semantics/altIdentifier/eissn/1867-3899Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:10256/235842026-05-29T05:05:01Z
dc.title.none.fl_str_mv A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
title A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
spellingShingle A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
Kasper, Johann B.
Oxidació
Oxidation
Alquens
Alkenes
title_short A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
title_full A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
title_fullStr A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
title_full_unstemmed A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
title_sort A Common Active Intermediate in the Oxidation of Alkenes, Alcohols and Alkanes with H2O2 and a Mn(II)/Pyridin-2-Carboxylato Catalyst
dc.creator.none.fl_str_mv Kasper, Johann B.
Saisaha, Pattama
Roo, Maurits de
Groen, Mitchell J.
Vicens Serra, Laia
Borrell Recasens, Margarida
Boer, Johannes W. de
Hage, Ronald
Costas Salgueiro, Miquel
Browne, Wesley R.
author Kasper, Johann B.
author_facet Kasper, Johann B.
Saisaha, Pattama
Roo, Maurits de
Groen, Mitchell J.
Vicens Serra, Laia
Borrell Recasens, Margarida
Boer, Johannes W. de
Hage, Ronald
Costas Salgueiro, Miquel
Browne, Wesley R.
author_role author
author2 Saisaha, Pattama
Roo, Maurits de
Groen, Mitchell J.
Vicens Serra, Laia
Borrell Recasens, Margarida
Boer, Johannes W. de
Hage, Ronald
Costas Salgueiro, Miquel
Browne, Wesley R.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Oxidació
Oxidation
Alquens
Alkenes
topic Oxidació
Oxidation
Alquens
Alkenes
description The mechanism and the reactive species involved in the oxidation of alkenes, and alcohols with H2O2, catalysed by an in situ prepared mixture of a MnII salt, pyridine-2-carboxylic acid and a ketone is elucidated using substrate competition experiments, kinetic isotope effect (KIE) measurements, and atom tracking with 18O labelling. The data indicate that a single reactive species engages in the oxidation of both alkenes and alcohols. The primary KIE in the oxidation of benzyl alcohols is ca. 3.5 and shows the reactive species to be selective despite a zero order dependence on substrate concentration, and the high turnover frequencies (up to 30 s−1) observed. Selective 18O labelling identifies the origin of the oxygen atoms transferred to the substrate during oxidation, and is consistent with a highly reactive, e. g., [MnV(O)(OH)] or [MnV(O)2], species rather than an alkylperoxy or hydroperoxy species
publishDate 2023
dc.date.none.fl_str_mv 2023
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/10256/23584
http://hdl.handle.net/10256/23584
url http://hdl.handle.net/10256/23584
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/cctc.202201072
info:eu-repo/semantics/altIdentifier/issn/1867-3880
info:eu-repo/semantics/altIdentifier/eissn/1867-3899
dc.rights.none.fl_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv ChemCatChem, 2023, vol. 15, núm. 1, p. e202201072
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 15,811543

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