Csp2–H Amination Reactions Mediated by Metastable Pseudo-Oh Masked Aryl-CoIII-nitrene Species
dc.contributor.author
dc.date.accessioned
2022-09-28T07:08:30Z
dc.date.available
2022-09-28T07:08:30Z
dc.date.issued
2022-08-23
dc.identifier.issn
0020-1669
dc.identifier.uri
dc.description.abstract
Cobalt-catalyzed C–H amination via M-nitrenoid species is spiking the interest of the research community. Understanding this process at a molecular level is a challenging task, and here we report a well-defined macrocyclic system featuring a pseudo-Oh aryl-CoIII species that reacts with aliphatic azides to effect intramolecular Csp2–N bond formation. Strikingly, a putative aryl-Co═NR nitrenoid intermediate species is formed and is rapidly trapped by a carboxylate ligand to form a carboxylate masked-nitrene, which functions as a shortcut to stabilize and guide the reaction to productive intramolecular Csp2–N bond formation. On one hand, several intermediate species featuring the Csp2–N bond formed have been isolated and structurally characterized, and the essential role of the carboxylate ligand has been proven. Complementarily, a thorough density functional theory study of the Csp2–N bond formation mechanism explains at the molecular level the key role of the carboxylate-masked nitrene species, which is essential to tame the metastability of the putative aryl-CoIII═NR nitrene species to effectively yield the Csp2–N products. The solid molecular mechanistic scheme determined for the Csp2–N bond forming reaction is fully supported by both experimental and computation complementary studies
dc.description.sponsorship
This work was financially supported by MICINN (CTQ2016-
77989-P and PID2019-104498GB-I00 to X.R., PGC2018-
098212-B-C22 to J.M.L. and PGC2018-095808-B-I00 to T.P.)
and Generalitat de Catalunya (2017SGR264 to X.R. and
2017SGR39 to J.M.L.)
Open Access funding provided thanks to the CRUE-CSIC agreement with ACS
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
PID2019-104498GB-I00
PGC2018-098212-B-C22
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Reproducció digital del document publicat a: https://doi.org/10.1021/acs.inorgchem.2c02111
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Inorganic Chemistry, 2022, vol. 61, núm. 35, p. 14075-14085
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Articles publicats (D-Q)
dc.rights
Attribution 4.0 International
dc.rights.uri
dc.title
Csp2–H Amination Reactions Mediated by Metastable Pseudo-Oh Masked Aryl-CoIII-nitrene Species
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/PID2019-104498GB-I00/ES/NANOCAPSULAS COMO PLATAFORMAS SUPRAMOLECULARES PARA LA FUNCIONALIZACION REGIOSELECTIVA DE FULLERENOS Y CATALISIS EN EL ESPACIO CONFINADO/
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-098212-B-C22/ES/DESCOMPOSICION EN EL ESPACIO REAL DE PROPIEDADES OPTICAS NO LINEALES PARA EL DISEÑO RACIONAL DE MATERIALES OPTOELECTRONICOS/
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-510X