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C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands |
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| Authors: | Jérémy Jacquet Pauline Chaumont Geoffrey Gontard Dr Maylis Orio Dr Hervé Vezin Dr Sébastien Blanchard Dr Marine Desage‐El?Murr Prof Louis Fensterbank |
| Affiliation: | 1. Sorbonne Universités, UPMC, Université Paris 06, UMR CNRS 8232, Institut Parisien de Chimie Moléculaire, France;2. Aix Marseille Université, CNRS, Centrale Marseille, iSm2 UMR 7313, Marseille cedex 20, France;3. Laboratoire de Spectrochimie Infrarouge et Raman, Université des Sciences et Technologies de Lille, UMR CNRS 8516, Villeneuve O'Ascq Cedex, France |
| Abstract: | 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. |
| Keywords: | copper density functional calculations ligand effects reaction mechanisms redox chemistry |
