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Metal‐Free Electrochemical Reduction of Carbon Dioxide Mediated by Cyclic(Alkyl)(Amino) Carbenes
Author(s) -
Lieske Lauren E.,
Freeman Lucas A.,
Wang Guocang,
Dickie Diane A.,
Gilliard Robert J.,
Machan Charles W.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201900316
Subject(s) - chemistry , electrochemical reduction of carbon dioxide , ketene , adduct , disproportionation , alkyl , carbon dioxide , redox , carbon monoxide , reagent , electrochemistry , photochemistry , inorganic chemistry , organic chemistry , catalysis , electrode
Carbenes are known to activate carbon dioxide to form zwitterionic adducts. Their inherent metal‐free redox activity remains understudied. Herein, we demonstrate that zwitterionic adducts of carbon dioxide formed with cyclic(alkyl)(amino) carbenes are not only redox active, but they can mediate the stoichiometric reductive disproportionation of carbon dioxide to carbon monoxide and carbonate. Infrared spectroelectrochemical experiments show that the reaction proceeds through an intermediate radical anion formed by one‐electron reduction, ultimately generating a ketene product and carbonate in the absence of additional organic or inorganic reagents.