Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes
Abstract
Electrocatalytic CO2 reduction is demonstrated for the Mn and Re tricarbonyl complexes, [M(Me2OQN)(CO)3(CH3CN)] (M = Mn or Re) containing the 5,7-dimethyl-8-oxyquinolate (Me2OQN–) ligand. In comparison to the related 2,2'-bipyridyl (bpy) reference complexes, [M(bpy)(CO)3(CH3CN)]+ (M = Mn or Re), the Me2OQN–-based precatalysts exhibit an onset of catalytic current with the input of one less equivalent of electrons. Furthermore, this behavior is attributed to the formal Me2OQN(•/–) redox couple which contributes toward each catalytic cycle in tandem with the formal Mn(I/0) and Re(I/0) redox couples. In addition to computational support for synergistic metal–ligand redox cooperativity, electrochemistry (cyclic voltammetry and controlled potential electrolysis), spectroelectrochemistry (FTIR and EPR), and pulse radiolysis coupled with time-resolved infrared spectroscopy (PR-TRIR) provide structural insight into the electronic properties of the one-electron- and two-electron-reduced species..
- Authors:
-
[2];
[3];
[3];
[1]
- Univ. of Massachusetts, Boston, MA (United States)
- Freie Univ. Berlin, Berlin (Germany)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1508524
- Report Number(s):
- BNL-211572-2019-JAAM
Journal ID: ISSN 0276-7333
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 38; Journal Issue: 6; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Citation Formats
McKinnon, Meaghan, Ngo, Ken T., Sobottka, Sebastian, Sarkar, Biprajit, Ertem, Mehmed Z., Grills, David C., and Rochford, Jonathan. Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes. United States: N. p., 2018.
Web. doi:10.1021/acs.organomet.8b00584.
McKinnon, Meaghan, Ngo, Ken T., Sobottka, Sebastian, Sarkar, Biprajit, Ertem, Mehmed Z., Grills, David C., & Rochford, Jonathan. Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes. United States. https://doi.org/10.1021/acs.organomet.8b00584
McKinnon, Meaghan, Ngo, Ken T., Sobottka, Sebastian, Sarkar, Biprajit, Ertem, Mehmed Z., Grills, David C., and Rochford, Jonathan. Thu .
"Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes". United States. https://doi.org/10.1021/acs.organomet.8b00584. https://www.osti.gov/servlets/purl/1508524.
@article{osti_1508524,
title = {Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes},
author = {McKinnon, Meaghan and Ngo, Ken T. and Sobottka, Sebastian and Sarkar, Biprajit and Ertem, Mehmed Z. and Grills, David C. and Rochford, Jonathan},
abstractNote = {Electrocatalytic CO2 reduction is demonstrated for the Mn and Re tricarbonyl complexes, [M(Me2OQN)(CO)3(CH3CN)] (M = Mn or Re) containing the 5,7-dimethyl-8-oxyquinolate (Me2OQN–) ligand. In comparison to the related 2,2'-bipyridyl (bpy) reference complexes, [M(bpy)(CO)3(CH3CN)]+ (M = Mn or Re), the Me2OQN–-based precatalysts exhibit an onset of catalytic current with the input of one less equivalent of electrons. Furthermore, this behavior is attributed to the formal Me2OQN(•/–) redox couple which contributes toward each catalytic cycle in tandem with the formal Mn(I/0) and Re(I/0) redox couples. In addition to computational support for synergistic metal–ligand redox cooperativity, electrochemistry (cyclic voltammetry and controlled potential electrolysis), spectroelectrochemistry (FTIR and EPR), and pulse radiolysis coupled with time-resolved infrared spectroscopy (PR-TRIR) provide structural insight into the electronic properties of the one-electron- and two-electron-reduced species..},
doi = {10.1021/acs.organomet.8b00584},
journal = {Organometallics},
number = 6,
volume = 38,
place = {United States},
year = {Thu Oct 11 00:00:00 EDT 2018},
month = {Thu Oct 11 00:00:00 EDT 2018}
}
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Figure 1: Molecular structures of [M(bpy)(CO)3(CH3CN)]+ ([1-M-MeCN]+, M = Re(I) or Mn(I)) and [M(Me2OQN)(CO)3(CH3CN)] ([2-M-MeCN], M = Re(I) or Mn(I)).
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