Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study

The Ni-catalyzed trifluoromethylthiolation of aryl halides with [NMe4][SCF3] has been studied with DFT methodology to find out the mechanism governing the reaction. Two different cross-coupling pathways have been explored; the first one, involving the classical Ni(0)/Ni(II) catalytic cycle, does not...

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Autor: Jover Modrego, Jesús
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/143543
Acceso en línea:https://hdl.handle.net/2445/143543
Access Level:acceso abierto
Palabra clave:Níquel
Catàlisi
Nickel
Catalysis
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spelling Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT studyJover Modrego, JesúsNíquelCatàlisiNickelCatalysisThe Ni-catalyzed trifluoromethylthiolation of aryl halides with [NMe4][SCF3] has been studied with DFT methodology to find out the mechanism governing the reaction. Two different cross-coupling pathways have been explored; the first one, involving the classical Ni(0)/Ni(II) catalytic cycle, does not provide a good explanation for the experimental outcomes. In contrast, an alternative Ni(I)/Ni(III) catalytic cycle affords a much better agreement with what is observed experimentally: a low reaction barrier that allows the reaction to work at room temperature for aryl iodides, and an interpretation of the reactivity for other aryl halides and substituted iodobenzenes. The active Ni(I) catalyst is generated through a two-step process consisting of a singlet to triplet transformation of the initial nickel species followed by a subsequent halogen atom transfer from the aryl halide.Royal Society of Chemistry2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/143543Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1039/C9CY01365BCatalysis Science & Technology, 2019, num. 21, p. 5962-5970https://doi.org/10.1039/C9CY01365B(c) Jover Modrego, Jesús, 2019info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1435432026-05-27T06:46:51Z
dc.title.none.fl_str_mv Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
title Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
spellingShingle Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
Jover Modrego, Jesús
Níquel
Catàlisi
Nickel
Catalysis
title_short Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
title_full Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
title_fullStr Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
title_full_unstemmed Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
title_sort Nickel-catalyzed aryl trifluoromethyl sulfides synthesis: A DFT study
dc.creator.none.fl_str_mv Jover Modrego, Jesús
author Jover Modrego, Jesús
author_facet Jover Modrego, Jesús
author_role author
dc.subject.none.fl_str_mv Níquel
Catàlisi
Nickel
Catalysis
topic Níquel
Catàlisi
Nickel
Catalysis
description The Ni-catalyzed trifluoromethylthiolation of aryl halides with [NMe4][SCF3] has been studied with DFT methodology to find out the mechanism governing the reaction. Two different cross-coupling pathways have been explored; the first one, involving the classical Ni(0)/Ni(II) catalytic cycle, does not provide a good explanation for the experimental outcomes. In contrast, an alternative Ni(I)/Ni(III) catalytic cycle affords a much better agreement with what is observed experimentally: a low reaction barrier that allows the reaction to work at room temperature for aryl iodides, and an interpretation of the reactivity for other aryl halides and substituted iodobenzenes. The active Ni(I) catalyst is generated through a two-step process consisting of a singlet to triplet transformation of the initial nickel species followed by a subsequent halogen atom transfer from the aryl halide.
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/143543
url https://hdl.handle.net/2445/143543
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1039/C9CY01365B
Catalysis Science & Technology, 2019, num. 21, p. 5962-5970
https://doi.org/10.1039/C9CY01365B
dc.rights.none.fl_str_mv (c) Jover Modrego, Jesús, 2019
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Jover Modrego, Jesús, 2019
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.300724

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