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Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction

Chapovetsky, Alon and Welborn, Matthew and Luna, M. and Haiges, Ralf and Miller, Thomas F., III and Marinescu, Smaranda C. (2018) Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO₂ Reduction. ACS Central Science, 4 (3). pp. 397-404. ISSN 2374-7943. PMCID PMC5879468. doi:10.1021/acscentsci.7b00607.

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The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO₂ to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO₂ reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO₂, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO₂, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO₂ substrate.

Item Type:Article
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URLURL TypeDescription Information CentralArticle
Chapovetsky, Alon0000-0001-8095-8830
Welborn, Matthew0000-0001-8659-6535
Haiges, Ralf0000-0003-4151-3593
Miller, Thomas F., III0000-0002-1882-5380
Marinescu, Smaranda C.0000-0003-2106-8971
Additional Information:© 2018 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: December 19, 2017. Published: February 23, 2018. This work was supported by the University of Southern California and the National Science Foundation (NSF) through the CAREER award (CHE-1555387) and the Chemistry of Life Processes Program (CHE-1611581). This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. We are grateful to the USC Wrigley Institute for a Norma and Jerol Sonosky summer fellowship to A.C. M.W. thanks the Resnick Sustainability Institute for a postdoctoral fellowship. We are grateful to NSF (Grant CRIF 1048807) and USC for their sponsorship of NMR spectrometers and an X-ray diffractometer. A.C. and M.W.: equal contribution. CCDC 1590218–1590221 contain the supplementary crystallographic data for this manuscript. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute, JCAP
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
Department of Energy (DOE)DE-SC0004993
University of Southern CaliforniaUNSPECIFIED
Issue or Number:3
PubMed Central ID:PMC5879468
Record Number:CaltechAUTHORS:20180315-111119688
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Official Citation:Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction Alon Chapovetsky, Matthew Welborn, John M. Luna, Ralf Haiges, Thomas F. Miller III, and Smaranda C. Marinescu ACS Central Science 2018 4 (3), 397-404 DOI: 10.1021/acscentsci.7b00607
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85331
Deposited By: Heidi Rusina
Deposited On:15 Mar 2018 19:57
Last Modified:15 Mar 2022 21:00

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