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. 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..
| Original language | English |
|---|---|
| Journal | Organometallics |
| DOIs | |
| Publication status | Accepted/In press - Jan 1 2018 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
Cite this
Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes. / McKinnon, Meaghan; Ngo, Ken T.; Sobottka, Sebastian; Sarkar, Biprajit; Ertem, Mehmed Z.; Grills, David; Rochford, Jonathan.
In: Organometallics, 01.01.2018.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes
AU - McKinnon, Meaghan
AU - Ngo, Ken T.
AU - Sobottka, Sebastian
AU - Sarkar, Biprajit
AU - Ertem, Mehmed Z.
AU - Grills, David
AU - Rochford, Jonathan
PY - 2018/1/1
Y1 - 2018/1/1
N2 - 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. 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..
AB - 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. 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..
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U2 - 10.1021/acs.organomet.8b00584
DO - 10.1021/acs.organomet.8b00584
M3 - Article
JO - Organometallics
JF - Organometallics
SN - 0276-7333
ER -