Circumventing Intrinsic Metal Reactivity: ...
Document type :
Article dans une revue scientifique
DOI :
Permalink :
Title :
Circumventing Intrinsic Metal Reactivity: Radical Generation with Redox-Active Ligands
Author(s) :
Jacquet, Jérémy [Auteur]
Cheaib, Khaled [Auteur]
Ren, Yufeng [Auteur]
Vezin, Herve [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE]
Orio, Maylis [Auteur]
Institut des Sciences Moléculaires de Marseille [ISM2]
Blanchard, Sébastien [Auteur]
Fensterbank, Louis [Auteur]
Desage-El Murr, Marine [Auteur]
Cheaib, Khaled [Auteur]
Ren, Yufeng [Auteur]
Vezin, Herve [Auteur]

Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE]
Orio, Maylis [Auteur]

Institut des Sciences Moléculaires de Marseille [ISM2]
Blanchard, Sébastien [Auteur]
Fensterbank, Louis [Auteur]
Desage-El Murr, Marine [Auteur]
Journal title :
Chemistry - A European Journal
Abbreviated title :
Chem. Eur. J.
Volume number :
23
Pages :
15030-15034
Publisher :
Wiley
Publication date :
2017-10-09
ISSN :
0947-6539
English keyword(s) :
CF3. radicals
nickel
redox-active ligand
single electron transfer
nickel
redox-active ligand
single electron transfer
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
Chimie/Chimie de coordination
Chimie/Catalyse
Chimie/Chimie de coordination
Chimie/Catalyse
English abstract : [en]
Nickel complexes have gained sustained attention as efficient catalysts in cross-coupling reactions and co-catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's ...
Show more >Nickel complexes have gained sustained attention as efficient catalysts in cross-coupling reactions and co-catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's propensity to shuttle through several accessible redox states from Ni0 to NiIV. Here, we report the catalytic generation of trifluoromethyl radicals from a nickel complex bearing redox-active iminosemiquinone ligands. This unprecedented reactivity is enabled through ligand-based oxidation performing electron transfer to an electrophilic CF3+ source while the nickel oxidation state is preserved. Additionally, extension of this reactivity to a copper complex bearing a single redox equivalent is reported, thus providing a unified reactivity scheme. These results open new pathways in radical chemistry with redox-active ligands.Show less >
Show more >Nickel complexes have gained sustained attention as efficient catalysts in cross-coupling reactions and co-catalysts in dual systems due to their ability to react with radical species. Central to this reactivity is nickel's propensity to shuttle through several accessible redox states from Ni0 to NiIV. Here, we report the catalytic generation of trifluoromethyl radicals from a nickel complex bearing redox-active iminosemiquinone ligands. This unprecedented reactivity is enabled through ligand-based oxidation performing electron transfer to an electrophilic CF3+ source while the nickel oxidation state is preserved. Additionally, extension of this reactivity to a copper complex bearing a single redox equivalent is reported, thus providing a unified reactivity scheme. These results open new pathways in radical chemistry with redox-active ligands.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
Administrative institution(s) :
Université de Lille
CNRS
CNRS
Collections :
Research team(s) :
Propriétés magnéto structurales des matériaux (PMSM)
Submission date :
2021-06-17T13:23:57Z
2021-06-24T12:27:46Z
2021-06-24T12:27:46Z
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