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Title: Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO 2 Reduction

Abstract

The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO 2 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 CO 2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO 2, 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 CO 2, 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 CO 2 substrate.

Authors:
 [1];  [2];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  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 Inst. 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.
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. doi:10.1021/acscentsci.7b00607.
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. doi:10.1021/acscentsci.7b00607. https://www.osti.gov/servlets/purl/1498679.
@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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Cited by: 39 works
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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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Works referencing / citing this record:

Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO 2 Reduction of Iron Porphyrins
journal, February 2019

  • Gotico, Philipp; Boitrel, Bernard; Guillot, Régis
  • Angewandte Chemie International Edition, Vol. 58, Issue 14
  • DOI: 10.1002/anie.201814339

Metallo-supramolecular assembly of protic pincer-type complexes: encapsulation of dinitrogen and carbon disulfide into a multiproton-responsive diruthenium cage
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  • Toda, Tatsuro; Suzuki, Satoshi; Kuwata, Shigeki
  • Chemical Communications, Vol. 55, Issue 8
  • DOI: 10.1039/c8cc08384c

A 2,2′-bipyridine-containing covalent organic framework bearing rhenium( i ) tricarbonyl moieties for CO 2 reduction
journal, January 2018

  • Popov, Damir A.; Luna, John M.; Orchanian, Nicholas M.
  • Dalton Transactions, Vol. 47, Issue 48
  • DOI: 10.1039/c8dt00125a

Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate
journal, January 2019

  • Roy, Lisa; Al-Afyouni, Malik H.; DeRosha, Daniel E.
  • Chemical Science, Vol. 10, Issue 3
  • DOI: 10.1039/c8sc02599a

Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines
journal, January 2019

  • Liao, Qian; Liu, Tianbiao; Johnson, Samantha I.
  • Dalton Transactions, Vol. 48, Issue 15
  • DOI: 10.1039/c9dt00708c

Elucidating the origins of enhanced CO 2 reduction in manganese electrocatalysts bearing pendant hydrogen-bond donors
journal, January 2019

  • Tignor, Steven E.; Shaw, Travis W.; Bocarsly, Andrew B.
  • Dalton Transactions, Vol. 48, Issue 33
  • DOI: 10.1039/c9dt02060h

Rhenium bipyridine catalysts with hydrogen bonding pendant amines for CO 2 reduction
journal, January 2019

  • Hellman, Ashley N.; Haiges, Ralf; Marinescu, Smaranda C.
  • Dalton Transactions, Vol. 48, Issue 38
  • DOI: 10.1039/c9dt02689d

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