{ "dc.contributor.author": "Pagès-Vilà, Neus" , "dc.contributor.author": "Gamba, Ilaria" , "dc.contributor.author": "Clémancey, Martin" , "dc.contributor.author": "Latour, Jean Marc" , "dc.contributor.author": "Company Casadevall, Anna" , "dc.contributor.author": "Costas Salgueiro, Miquel" , "dc.date.accessioned": "2024-07-02T06:10:01Z" , "dc.date.available": "2024-07-02T06:10:01Z" , "dc.date.issued": "2024-10" , "dc.identifier.issn": "0162-0134" , "dc.identifier.uri": "http://hdl.handle.net/10256/25065" , "dc.description.abstract": "Halogenation of aliphatic C–H bonds is a chemical transformation performed in nature by mononuclear nonheme iron dependent halogenases. The mechanism involves the formation of an iron(IV)-oxo-chloride species that abstracts the hydrogen atom from the reactive C–H bond to form a carbon-centered radical that selectively reacts with the bound chloride ligand, a process commonly referred to as halide rebound. The factors that determine the halide rebound, as opposed to the reaction with the incipient hydroxide ligand, are not clearly understood and examples of well-defined iron(IV)-oxo-halide compounds competent in C–H halogenation are scarce. In this work we have studied the reactivity of three well-defined iron(IV)-oxo complexes containing variants of the tetradentate 1-(2-pyridylmethyl)-1,4,7-triazacyclononane ligand (Pytacn). Interestingly, these compounds exhibit a change in their chemoselectivity towards the functionalization of C–H bonds under certain conditions: their reaction towards C–H bonds in the presence of a halide anionleads to exclusive oxygenation, while the addition of a superacid results in halogenation. Almost quantitative halogenation of ethylbenzene is observed when using the two systems with more sterically congested ligands and even the chlorination of strong C–H bonds such as those of cyclohexane is performed when a methyl group is present in the sixth position of the pyridine ring of the ligand. Mechanistic studies suggest that both reactions, oxygenation and halogenation, proceed through a common rate determining hydrogen atom transfer step and the presence of the acid dictates the fate of the resulting alkyl radical towards preferential halogenation over oxygenation" , "dc.description.sponsorship": "The authors thank the Spanish Ministry of Science (PID2019-106699GB-I00 to A.C. and PID2021-129036NB-I00 to M.C.) and Generalitat de Catalunya (ICREA Academia Award and 2021SGR00475 project to M.C. and A.C.) for financial support. M.C. thanks financial support from the European Research Council (ERC-2019-ADG-883922)" , "dc.description.sponsorship": "Open Access funding provided thanks to the CRUE-CSIC agreement with Elsevier" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "Elsevier" , "dc.relation": "PID2019-106699GB-I00" , "dc.relation": "PID2021-129036NB-I00" , "dc.relation.isformatof": "Reproducció digital del document publicat a: https://doi.org/10.1016/j.jinorgbio.2024.112643" , "dc.relation.ispartof": "Journal of Inorganic Biochemistry, 2024, vol. 259, art.núm. 112643" , "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": "Halogenació" , "dc.subject": "Halogenation" , "dc.subject": "Reaccions químiques" , "dc.subject": "Chemical reactions" , "dc.title": "Proton-triggered chemoselective halogenation of aliphatic C–H bonds with nonheme FeIV-oxo complexes" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/openAccess" , "dc.relation.projectID": "info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106699GB-I00/ES/LIGANDOS NO INOCENTES COMO PLATAFORMAS PARA LA FUNCIONALIZACION DE ENLACES C-H Y C=C CON GRUPOS OXO, NITRENO Y CARBENO/" , "dc.relation.projectID": "info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-129036NB-I00/ES/CATALIZADORES MOLECULARES BIOINSPIRADOS PARA LA FUNCIONALIZACION ESTEREOSELECTIVA DE ENLACES SP2 Y SP3 C-H/" , "dc.relation.projectID": "info:eu-repo/grantAgreement/EC/H2020/883922/EU/Enantioselective C-H Oxidation Guided by Rational Catalyst Design/ECHO-GRACADE" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "https://doi.org/10.1016/j.jinorgbio.2024.112643" , "dc.identifier.idgrec": "038933" , "dc.contributor.funder": "Agencia Estatal de Investigación" , "dc.contributor.funder": "European Commission" , "dc.type.peerreviewed": "peer-reviewed" , "dc.relation.FundingProgramme": "Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020" , "dc.relation.FundingProgramme": "Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023" , "dc.relation.FundingProgramme": "H2020" , "dc.relation.ProjectAcronym": "LIGANDOS NO INOCENTES COMO PLATAFORMAS PARA LA FUNCIONALIZACION DE ENLACES C-H Y C=C CON GRUPOS OXO, NITRENO Y CARBENO" , "dc.relation.ProjectAcronym": "CATALIZADORES MOLECULARES BIOINSPIRADOS PARA LA FUNCIONALIZACION ESTEREOSELECTIVA DE ENLACES SP2 Y SP3 C-H" , "dc.relation.ProjectAcronym": "ECHO-GRACADE" , "dc.identifier.eissn": "1873-3344" }