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

Meaghan McKinnon, Ken T. Ngo, Sebastian Sobottka, Biprajit Sarkar, Mehmed Z. Ertem, David Grills, Jonathan Rochford

Research output: Contribution to journalArticle

3 Citations (Scopus)

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 languageEnglish
JournalOrganometallics
DOIs
Publication statusAccepted/In press - Jan 1 2018

Fingerprint

2,2'-Dipyridyl
Metals
Carbon Monoxide
Ligands
ligands
Electrons
metals
Spectroelectrochemistry
Radiolysis
electrons
Electrochemistry
electrolysis
electrochemistry
radiolysis
Electrolysis
Electronic properties
Cyclic voltammetry
Paramagnetic resonance
Infrared spectroscopy
infrared spectroscopy

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 journalArticle

McKinnon, Meaghan ; Ngo, Ken T. ; Sobottka, Sebastian ; Sarkar, Biprajit ; Ertem, Mehmed Z. ; Grills, David ; Rochford, Jonathan. / Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes. In: Organometallics. 2018.
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