Valence Localization at a Bio-inspired Mixed-Valent {Cu 2 S} 2+ Motif upon Solvation in Acetonitrile: Effect on Nitrous Oxide Reductase (N 2 Or) Activity

Charlène Esmieu (1) , Maylis Orio (2, 3) , Jordan Mangue (1) , Jacques Pécaut (4) , Stéphane Ménage (1) , Stéphane Torelli (1)

1 LCBM - UMR 5249 - Laboratoire de Chimie et Biologie des Métaux
2 ISM2 - Institut des Sciences Moléculaires de Marseille
3 LASIRE - Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516
4 CIBEST - Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie

We demonstrate, based on experimental and theoretical evidence, that the isolated [2(CH3CN)2]2+ complex prepared in CH3CN and containing a mixed‐valent {Cu2II,IS} core evolves towards a new [2(CH3CN)3]2+ species upon solvation in CH3CN. Unlike its type III structural analogue [2(H2O)(OTf)]+ active toward N2O reduction, this new type I compound is inactive. This outcome opens new perspectives for a rational for N2O activation using bio‐inspired Cu/S complexes, especially on the role of the valence localization/delocalization and the Cu−Cu bond on the reactivity.

Domaines: Chimie

Charlène Esmieu, Maylis Orio, Jordan Mangue, Jacques Pécaut, Stéphane Ménage, et al.. Valence Localization at a Bio-inspired Mixed-Valent {Cu 2 S} 2+ Motif upon Solvation in Acetonitrile: Effect on Nitrous Oxide Reductase (N 2 Or) Activity. Chemistry - A European Journal, 2018, 24 (20), pp.5060 - 5063. ⟨10.1002/chem.201704737⟩. ⟨hal-01771018⟩