Copper–Ligand Cooperativity in H2 Activation Enables the Synthesis of Copper Hydride Complexes

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 )­(H...

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Bibliographic Details
Published inOrganometallics Vol. 40; no. 13; pp. 2064 - 2069
Main Authors Aloisi, Alicia, Crochet, Étienne, Nicolas, Emmanuel, Berthet, Jean-Claude, Lescot, Camille, Thuéry, Pierre, Cantat, Thibault
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 12.07.2021
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
KETONES
DEHYDROGENATION
FORMATE
CATALYTIC-HYDROGENATION
CRYSTALLOGRAPHIC CHARACTERIZATION
CO2 HYDROGENATION
REACTIVITY
METAL-HYDRIDES
CARBON-DIOXIDE
DERIVATIVES
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Summary: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 the 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)]. A QTAIM (quantum theory of atoms in molecules) analysis of the Cu–H–BEt3 interaction indicates a hydride complex stabilized by the Lewis acid BEt3.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.1c00212