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  Mechanistic Insights into the Electrochemical Reduction of CO2 Catalyzed by Iron Cyclopentadienone Complexes

Oberem, E., Roesel, A. F., Rosas-Hernández, A., Kull, T., Fischer, S., Spannenberg, A., et al. (2019). Mechanistic Insights into the Electrochemical Reduction of CO2 Catalyzed by Iron Cyclopentadienone Complexes. Organometallics, 38(6), 1236-1247. doi:10.1021/acs.organomet.8b00517.

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 Creators:
Oberem, Elisabeth1, 2, Author
Roesel, Arend F.3, Author
Rosas-Hernández, Alonso2, Author
Kull, Tobias4, 5, Author              
Fischer, Steffen1, 3, Author
Spannenberg, Anke2, Author
Junge, Henrik2, Author
Beller, Matthias2, Author
Ludwig, Ralf1, 2, Author
Roemelt, Michael4, 5, Author              
Francke, Robert3, Author
Affiliations:
1LL&M Department, Rostock University, Albert-Einstein-Straße 25, 18059 Rostock, Germany, ou_persistent22              
2Leibniz Institute for Catalysis, Albert-Einstein-Straße 29a, 18059 Rostock, Germany, ou_persistent22              
3Institute of Chemistry, Rostock University, Albert-Einstein-Straße 3a, 18059 Rostock, Germany, ou_persistent22              
4Chair for Theoretical Chemistry, Ruhr-University Bochum, 44780 Bochum, Germany, ou_persistent22              
5Research Group Roemelt, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_3018043              

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 Abstract: In a previous paper we have demonstrated that the easily-synthesized class of iron(0) cyclopentadienone complexes constitutes a promising catalyst platform for the electrochemical conversion of CO2 to CO and H2O. One of the unusual features of these catalysts is that catalysis proceeds efficiently in aprotic electrolytes in the absence of acidic additives. Herein we present a detailed study of the underlying catalytic mechanisms. Using a combination of FTIR spectroelectrochemistry, DFT calculations, and nonelectrochemical control experiments, we have identified a number of catalytic intermediates including the active species and the product of catalyst deactivation. On the basis of these insights, we have carried out digital simulations in order to decipher the voltammetric profiles of the iron(0) cyclopentadienones. Further control experiments revealed that the anodic oxidation of the electrolyte constitutes the terminal proton source for the formation of CO and H2O. Taken together, our results suggest a competition between two coexisting catalytic pathways, one of which proceeds via a hitherto unknown Fe–Fe dimer as an active species.

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Language(s): eng - English
 Dates: 2018-07-232018-09-202019-03-25
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.organomet.8b00517
 Degree: -

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Title: Organometallics
  Other : Organometallics
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 38 (6) Sequence Number: - Start / End Page: 1236 - 1247 Identifier: ISSN: 0276-7333
CoNE: https://pure.mpg.de/cone/journals/resource/954925505259