Titre :

C−N Bond Formation from a Masked High-Valent Copper Complex Stabilized by Redox Non-Innocent Ligands

Auteur(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]

Titre de la revue :

Angewandte Chemie International Edition

Nom court de la revue :

Angew. Chem. Int. Ed.

Numéro :

55

Pagination :

10712-10716

Éditeur :

Wiley

Date de publication :

2016-08-09

ISSN :

1433-7851

Mot(s)-clé(s) en anglais :

redox chemistry
reaction mechanisms
copper
density functional calculations
ligand effects

Discipline(s) HAL :

Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

Résumé en anglais : [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, ...
Lire la suite >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.Lire moins >

Langue :

Anglais

Comité de lecture :

Oui

Audience :

Internationale

Vulgarisation :

Non

Établissement(s) :

Université de Lille
CNRS

Collections :

• Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516

Équipe(s) de recherche :

Propriétés magnéto structurales des matériaux (PMSM)

Date de dépôt :

2021-06-17T13:33:17Z
2021-06-24T08:58:43Z