Mediated Inner‐Sphere Electron Transfer Induces Homogeneous Reduction of CO 2 via Through‐Space Electronic Conjugation**

Hooe, Shelby L.; Moreno, Juan J.; Reid, Amelia G.; Cook, Emma N.; Machan, Charles W.

doi:10.1002/ange.202109645

Title: Mediated Inner‐Sphere Electron Transfer Induces Homogeneous Reduction of CO ₂ via Through‐Space Electronic Conjugation**

Journal Article · 09 November 2021 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202109645 · OSTI ID:1829755

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Department of Chemistry University of Virginia McCormick Road, PO Box 400319 Charlottesville VA 22904-4319 USA

Abstract The electrocatalytic reduction of CO ₂ is an appealing method for converting renewable energy sources into value‐added chemical feedstocks. We report a co‐electrocatalytic system for the reduction of CO ₂ to CO comprised of a molecular Cr complex and dibenzothiophene‐5,5‐dioxide (DBTD) as a redox mediator, which achieves high activity (TOF=1.51–2.84×10 ⁵ 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 CO ₂ 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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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0022219

OSTI ID:: 1829755

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 1 Vol. 134; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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