Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species
dc.contributor.author
dc.date.accessioned
2017-02-14T15:48:45Z
dc.date.available
2017-02-14T15:48:45Z
dc.date.issued
2016-11-02
dc.identifier.issn
1433-7851
dc.identifier.uri
dc.description
Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2016, vol.128, núm. 45, p. 14211–14214. DOI http://dx.doi.org/10.1002/ange.201607238
dc.description.abstract
High-valent terminal copper–nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions. The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous. Very recently, the Lewis acid adduct of a copper–nitrene intermediate was trapped at −90 °C and shown to be active in various oxidation reactions. Herein, we describe for the first time the synthesis and spectroscopic characterization of a terminal copper(II)–nitrene radical species that is stable at room temperature in the absence of any Lewis acid. The azide derivative of a triazamacrocyclic ligand that had previously been utilized in the stabilization of aryl–CuIII intermediates was employed as an ancillary ligand in the study. The terminal copper(II)–nitrene radical species is able to transfer a nitrene moiety to phosphines and abstract a hydrogen atom from weak C−H bonds, leading to the formation of oxidized products in modest yields
dc.description.sponsorship
This work was supported by the European Commission (2011-CIG-303522 to A.C.), the MINECO of Spain (“Ramón y Cajal” contract to A.C. and CTQ2013-43012-P to A.C. and X.R.), the Clara Immerwahr award of UniCat (to A.C.), the European Research Council (Starting Grant ERC-2011-StG-277801 to X.R.), and the Generalitat de Catalunya (2014 SGR 862)
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application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2013-43012-P/ES/INVESTIGACIONES MECANISTICAS PARA SINTESIS ORGANICA SOSTENIBLE VIA ACTIVACION DE PEQUEÑAS MOLECULAS GASEOSAS Y DE ENLACES C-H CON METALES DE LA PRIMERA SERIE DE TRANSICION/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1002/anie.201607238
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© Angewandte Chemie International Edition, 2016, vol. 55, núm. 45, p. 14005-14008
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
Characterization and Reactivity Studies of a Terminal Copper-Nitrene Species
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/303522/EU/Key insights into oxidation chemistry through synthetic systems: N2O activation with first-row transition-metals and O2 activation in heterobimetallic Fe-Ni systems/NEWOXMET
info:eu-repo/grantAgreement/EC/FP7/277801/EU/Sustainable C-X and C-H Functionalization Catalyzed by Copper(III) Species/SUSCATCU3
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
025894
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dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3773