Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation.
Angew Chem Int Ed Engl
; 61(1): e202109645, 2022 Jan 03.
Article
em En
| MEDLINE
| ID: mdl-34695281
ABSTRACT
The electrocatalytic reduction of CO2 is an appealing method for converting renewable energy sources into value-added chemical feedstocks. We report a co-electrocatalytic system for the reduction of CO2 to CO comprised of a molecular Cr complex and dibenzothiophene-5,5-dioxide (DBTD) as a redox mediator, which achieves high activity (TOF=1.51-2.84×105 â
s-1 ) and quantitative selectivity. Under aprotic or protic conditions, DBTD produces a co-electrocatalytic response with 1 by coordinating trans to the site of CO2 binding and mediating electron transfer from the electrode with quantitative efficiency for CO. This assembly is reliant on through-space electronic conjugation between the π frameworks of DBTD and the bpy fragment of the catalyst ligand, with contributions from dispersive interactions and weak sulfone coordination.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
Estados Unidos