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

Abstract

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.

Authors:
 [1];  [2];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
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  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1498679
Grant/Contract Number:  
SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chapovetsky, Alon, Welborn, Matthew, Luna, John M., Haiges, Ralf, Miller, Thomas F., and Marinescu, Smaranda C. Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction. United States: N. p., 2018. Web. doi:10.1021/acscentsci.7b00607.
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Chapovetsky, Alon, Welborn, Matthew, Luna, John M., Haiges, Ralf, Miller, Thomas F., & Marinescu, Smaranda C. Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction. United States. https://doi.org/10.1021/acscentsci.7b00607
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Chapovetsky, Alon, Welborn, Matthew, Luna, John M., Haiges, Ralf, Miller, Thomas F., and Marinescu, Smaranda C. Fri . "Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction". United States. https://doi.org/10.1021/acscentsci.7b00607. https://www.osti.gov/servlets/purl/1498679.
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@article{osti_1498679,
title = {Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO2 Reduction},
author = {Chapovetsky, Alon and Welborn, Matthew and Luna, John M. and Haiges, Ralf and Miller, Thomas F. and Marinescu, Smaranda C.},
abstractNote = {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.},
doi = {10.1021/acscentsci.7b00607},
journal = {ACS Central Science},
number = 3,
volume = 4,
place = {United States},
year = {2018},
month = {2}
}
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https://doi.org/10.1021/acscentsci.7b00607
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Figures / Tables:

Figure 1 Figure 1: Syntheses of complexes 1(II)−6(II). The oxidation state of the cobalt center in each complex is indicated by the superscript.
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