TY - JOUR
T1 - Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO 2 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 C.
AU - Rochford, Jonathan
PY - 2019/3/25
Y1 - 2019/3/25
N2 - Electrocatalytic CO 2 reduction is demonstrated for the Mn and Re tricarbonyl complexes, [M(Me 2 OQN)(CO) 3 (CH 3 CN)] (M = Mn or Re) containing the 5,7-dimethyl-8-oxyquinolate (Me 2 OQN - ) ligand. In comparison to the related 2,2′-bipyridyl (bpy) reference complexes, [M(bpy)(CO) 3 (CH 3 CN)] + (M = Mn or Re), the Me 2 OQN - -based precatalysts exhibit an onset of catalytic current with the input of one less equivalent of electrons. This behavior is attributed to the formal Me 2 OQN (•/-) 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 CO 2 reduction is demonstrated for the Mn and Re tricarbonyl complexes, [M(Me 2 OQN)(CO) 3 (CH 3 CN)] (M = Mn or Re) containing the 5,7-dimethyl-8-oxyquinolate (Me 2 OQN - ) ligand. In comparison to the related 2,2′-bipyridyl (bpy) reference complexes, [M(bpy)(CO) 3 (CH 3 CN)] + (M = Mn or Re), the Me 2 OQN - -based precatalysts exhibit an onset of catalytic current with the input of one less equivalent of electrons. This behavior is attributed to the formal Me 2 OQN (•/-) 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
AN - SCOPUS:85054994487
VL - 38
SP - 1317
EP - 1329
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 6
ER -