Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation**
Correction(s) for this article
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Corrigendum: Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation
- Volume 61Issue 25Angewandte Chemie International Edition
- First Published online: June 10, 2022
Shelby L. Hooe
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
These authors contributed equally to this work.
Search for more papers by this authorJuan J. Moreno
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
These authors contributed equally to this work.
Search for more papers by this authorAmelia G. Reid
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
Search for more papers by this authorEmma N. Cook
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
Search for more papers by this authorCorresponding Author
Charles W. Machan
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
Search for more papers by this authorShelby L. Hooe
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
These authors contributed equally to this work.
Search for more papers by this authorJuan J. Moreno
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
These authors contributed equally to this work.
Search for more papers by this authorAmelia G. Reid
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
Search for more papers by this authorEmma N. Cook
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
Search for more papers by this authorCorresponding Author
Charles W. Machan
Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA, 22904-4319 USA
Search for more papers by this authorA previous version of this manuscript has been deposited on a preprint server (https://doi.org/10.26434/chemrxiv.14165951.v1.).
Graphical Abstract
Through-space electronic conjugation between a redox mediator and molecular Cr complex enables emergent co-electrocatalytic activity for the electrochemical reduction of carbon dioxide to carbon monoxide. In the reduced forms, the aromatic portions interact through a combination of dispersion forces, π conjugation, and weak coordination of the sulfone to Cr.
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 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.
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