{ "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" }