{
"dc.contributor.author": "Sabeña Vila, Gerard"
,
"dc.contributor.author": "Gamba, Ilaria"
,
"dc.contributor.author": "Gómez Martín, Laura"
,
"dc.contributor.author": "Clémancey, Martin"
,
"dc.contributor.author": "Frisch, Jonathan R."
,
"dc.contributor.author": "Klinker, Eric J."
,
"dc.contributor.author": "Blondin, Geneviève"
,
"dc.contributor.author": "Torelli, Stephane"
,
"dc.contributor.author": "Que, Lawrence"
,
"dc.contributor.author": "Martin-Diaconescu, Vlad"
,
"dc.contributor.author": "Latour, Jean Marc"
,
"dc.contributor.author": "Lloret Fillol, Julio"
,
"dc.contributor.author": "Costas Salgueiro, Miquel"
,
"dc.date.accessioned": "2020-06-17T06:54:00Z"
,
"dc.date.available": "2020-06-17T06:54:00Z"
,
"dc.date.issued": "2019-08-20"
,
"dc.identifier.issn": "2041-6520"
,
"dc.identifier.uri": "http://hdl.handle.net/10256/18180"
,
"dc.description.abstract": "High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron(IV)–tosylimido complexes [FeIV(NTs)(MePy2tacn)](OTf)2 (1(IV)[double bond, length as m-dash]NTs) and [FeIV(NTs)(Me2(CHPy2)tacn)](OTf)2 (2(IV)[double bond, length as m-dash]NTs), (MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane, and Me2(CHPy2)tacn = 1-(di(2-pyridyl)methyl)-4,7-dimethyl-1,4,7-triazacyclononane, Ts = Tosyl). 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs are rare examples of octahedral iron(IV)–imido complexes and are isoelectronic analogues of the recently described iron(IV)–oxo complexes [FeIV(O)(L)]2+ (L = MePy2tacn and Me2(CHPy2)tacn, respectively). 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs are metastable and have been spectroscopically characterized by HR-MS, UV-vis, 1H-NMR, resonance Raman, Mössbauer, and X-ray absorption (XAS) spectroscopy as well as by DFT computational methods. Ferric complexes [FeIII(HNTs)(L)]2+, 1(III)–NHTs (L = MePy2tacn) and 2(III)–NHTs (L = Me2(CHPy2)tacn) have been isolated after the decay of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs in solution, spectroscopically characterized, and the molecular structure of [FeIII(HNTs)(MePy2tacn)](SbF6)2 determined by single crystal X-ray diffraction. Reaction of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs with different p-substituted thioanisoles results in the transfer of the tosylimido moiety to the sulphur atom producing sulfilimine products. In these reactions, 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs behave as single electron oxidants and Hammett analyses of reaction rates evidence that tosylimido transfer is more sensitive than oxo transfer to charge effects. In addition, reaction of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs with hydrocarbons containing weak C–H bonds results in the formation of 1(III)–NHTs and 2(III)–NHTs respectively, along with the oxidized substrate. Kinetic analyses indicate that reactions proceed via a mechanistically unusual HAT reaction, where an association complex precedes hydrogen abstraction"
,
"dc.description.sponsorship": "Financial support from the
Spanish Ministry of Science CTQ2015-70795-P (M. C.),
CTQ2016-80038-R (J. L. F.) and Generalitat de Catalunya (ICREA
Academia Award to M. C. and 2017 SGR 01378)"
,
"dc.format.mimetype": "application/pdf"
,
"dc.language.iso": "eng"
,
"dc.publisher": "Royal Society of Chemistry (RSC)"
,
"dc.relation": "info:eu-repo/grantAgreement/MINECO//CTQ2015-70795-P/ES/GENERACION Y CARACTERIZACION DE ESPECIES DE HIERRO Y MANGANESO EN ALTOS ESTADOS DE OXIDACION, Y SU USO EN CATALISIS ASIMETRICA/"
,
"dc.relation.isformatof": "Reproducció digital del document publicat a: https://doi.org/10.1039/c9sc02526j"
,
"dc.relation.ispartof": "Chemical Science, 2019,vol. 10, p. 9513-9529"
,
"dc.relation.ispartofseries": "Articles publicats (D-Q)"
,
"dc.rights": "Attribution-NonCommercial 4.0 International"
,
"dc.rights.uri": "http://creativecommons.org/licenses/by-nc/4.0/"
,
"dc.subject": "Ferro -- Compostos"
,
"dc.subject": "Iron compounds"
,
"dc.subject": "Reacció d'oxidació-reducció"
,
"dc.subject": "Oxidation-reduction reaction"
,
"dc.subject": "Oxidació"
,
"dc.subject": "Oxidation"
,
"dc.title": "Octahedral iron(IV)–tosylimido complexes exhibiting single electron-oxidation reactivity"
,
"dc.type": "info:eu-repo/semantics/article"
,
"dc.rights.accessRights": "info:eu-repo/semantics/openAccess"
,
"dc.type.version": "info:eu-repo/semantics/publishedVersion"
,
"dc.identifier.doi": "https://doi.org/10.1039/c9sc02526j"
,
"dc.identifier.idgrec": "031200"
,
"dc.contributor.funder": "Ministerio de Economía y Competitividad (Espanya)"
,
"dc.type.peerreviewed": "peer-reviewed"
,
"dc.relation.ProjectAcronym": "GENERACION Y CARACTERIZACION DE ESPECIES DE HIERRO Y MANGANESO EN ALTOS ESTADOS DE OXIDACION, Y SU USO EN CATALISIS ASIMETRICA"
,
"dc.identifier.eissn": "2041-6539"
}