Copper-Ligand Cooperativity in H$_2$ Activation Enables the Synthesis of Copper Hydride Complexes

Alicia Aloisi (1) , Étienne Crochet (1) , Emmanuel Nicolas (1) , Jean-Claude Berthet (1) , Camille Lescot (1) , Pierre Thuéry (1) , Thibault Cantat (1)

1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)

Copper(I) complexes of a new participative triphosphane ligand (2 H) have been prepared and structurally characterized, in particular [Cu(2 H)I] and [Cu(2)]2. Hydrogenation of the latter species afforded the trimetallic hydride species [Cu3(2)2(µ-H)] or in the presence of BEt3, [Cu(2 H)(HBEt3)]. Their formation evidences transient formation of [Cu(2 H)H] formed by hydrogenolysis of the Cu-N bond of [Cu(2)]2. [Cu(2 H)(HBEt3)] behaves like a hydride complex and inserts CO2 to yield the formate product [Cu(2 H)(O2CH)]. QTAIM analysis of the Cu-H-BEt3 interaction indicates a hydride complex stabilized by the Lewis acid BEt3.

Domaines: Chimie de coordination

Alicia Aloisi, Étienne Crochet, Emmanuel Nicolas, Jean-Claude Berthet, Camille Lescot, et al.. Copper-Ligand Cooperativity in H$_2$ Activation Enables the Synthesis of Copper Hydride Complexes. 2021. ⟨cea-03132894⟩