DUGiDocsExceedingly fast oxygen atom transfer to olefins via a catalytically competent nonheme iron species
dc.contributor.author
dc.date.accessioned
2016-11-22T12:28:37Z
dc.date.available
2016-11-22T12:28:37Z
dc.date.issued
2016-05-17
dc.identifier.issn
1433-7851
dc.identifier.uri
dc.description
El mateix article està publicat en alemany a l'edició alemanya d' 'Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 21, p.6418–6422. DOI http://dx.doi.org/10.1002/ange.201601396
dc.description.abstract
The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at −40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(O)(OAc)(PyNMe3)]2+, in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the substrate on the reaction rate could be elucidated, and the relative reactivities determined for the catalytic oxidations could be reproduced by kinetic studies. The observed fast reaction rates and high selectivities demonstrate that this metastable compound is a truly competent OAT intermediate of relevance for nonheme iron catalyzed epoxidations
dc.description.sponsorship
Financial support for this work was provided by the EuropeanCommission (2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), the Spanish Ministry of Science (CTQ2012-37420-C02-01/BQU to M.C., CTQ2012-37821-C02-02 to M.G.B., CTQ2013-43012-P to A.C., CTQ2013-48917-C3-1-P to R.B. and E.G.-E.), the Unidad de Excelencia (MDM 2015-0038 and CSD2010-00065 to M.C., M.G.B., R.B., and E.G.-E), the Generalitat Valenciana (PROMETEOII 2015/002t to R.B. and E.G.-E.), and the Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014SGR-862). The Spanish Ministry of Science is also acknowledged for a Ramýn y Cajal contract to A.C. (RYC-2011-08683)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/
MICINN/PN 2010-2016/CSD2010-00065
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/
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/anie.201601396
dc.relation.ispartof
© Angewandte Chemie - International Edition, 2016, vol. 55, núm. 22,p. 6310-6314
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Articles publicats (D-Q)
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Tots els drets reservats
dc.title
Exceedingly fast oxygen atom transfer to olefins via a catalytically competent nonheme iron 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/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
024883
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3773