C−N Bond Formation from a Masked High-Valent ...
Document type :
Article dans une revue scientifique
DOI :
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Title :
C−N Bond Formation from a Masked High-Valent Copper Complex Stabilized by Redox Non-Innocent Ligands
Author(s) :
Jacquet, Jérémy [Auteur]
Chaumont, Pauline [Auteur]
Gontard, Geoffrey [Auteur]
Orio, Maylis [Auteur]
Institut des Sciences Moléculaires de Marseille [ISM2]
Vezin, Herve [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE]
Blanchard, Sébastien [Auteur]
Desage-El Murr, Marine [Auteur]
Fensterbank, Louis [Auteur]
Chaumont, Pauline [Auteur]
Gontard, Geoffrey [Auteur]
Orio, Maylis [Auteur]

Institut des Sciences Moléculaires de Marseille [ISM2]
Vezin, Herve [Auteur]

Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE]
Blanchard, Sébastien [Auteur]
Desage-El Murr, Marine [Auteur]
Fensterbank, Louis [Auteur]
Journal title :
Angewandte Chemie International Edition
Abbreviated title :
Angew. Chem. Int. Ed.
Volume number :
55
Pages :
10712-10716
Publisher :
Wiley
Publication date :
2016-08-09
ISSN :
1433-7851
English keyword(s) :
redox chemistry
reaction mechanisms
copper
density functional calculations
ligand effects
reaction mechanisms
copper
density functional calculations
ligand effects
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
English abstract : [en]
The reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low-valent counterpart bearing reduced ligands, ...
Show more >The reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low-valent counterpart bearing reduced ligands, this complex performs high-yielding C−N bond formations. Mechanistic studies suggest that this behavior could stem from a mechanism akin to reductive elimination occurring at the metal center but facilitated by the ligand: it is proposed that a masked high oxidation state of the metal can be stabilized as a lower copper(II) oxidation state by the redox ligands without forfeiting its ability to behave as a high-valent copper(III) center. These observations are substantiated by a combination of advanced EPR spectroscopy techniques with DFT studies. This work sheds light on the potential of redox ligands as promoters of unusual reactivities at metal centers and illustrates the concept of masked high-valent metallic species.Show less >
Show more >The reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low-valent counterpart bearing reduced ligands, this complex performs high-yielding C−N bond formations. Mechanistic studies suggest that this behavior could stem from a mechanism akin to reductive elimination occurring at the metal center but facilitated by the ligand: it is proposed that a masked high oxidation state of the metal can be stabilized as a lower copper(II) oxidation state by the redox ligands without forfeiting its ability to behave as a high-valent copper(III) center. These observations are substantiated by a combination of advanced EPR spectroscopy techniques with DFT studies. This work sheds light on the potential of redox ligands as promoters of unusual reactivities at metal centers and illustrates the concept of masked high-valent metallic species.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 :
2021-06-17T13:33:17Z
2021-06-24T08:58:43Z
2021-06-24T08:58:43Z
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