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Synergistic Metal–Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes

Journal Article · · Organometallics
 [1];  [1];  [2];  [2];  [3];  [3];  [1]
  1. Univ. of Massachusetts, Boston, MA (United States)
  2. Freie Univ. Berlin, Berlin (Germany)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations
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..
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1508524
Report Number(s):
BNL--211572-2019-JAAM
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 6 Vol. 38; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

An Investigation of Electrocatalytic CO2 Reduction Using a Manganese Tricarbonyl Biquinoline Complex journal September 2019
Inter-ligand intramolecular through-space anisotropic shielding in a series of manganese carbonyl phosphorous compounds journal January 2019
Structural origins of the electronic properties of materials via time-resolved infrared spectroscopy journal January 2019

Figures / Tables (18)

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Scheme 1(p. 4)figure Scheme 1
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Scheme 2(p. 6)figure Scheme 2
Table 1(p. 6)table Table 1
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Figure 12(p. 12)figure Figure 12
Scheme 3(p. 13)figure Scheme 3

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY