Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO                         2                          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 C. Grills; Jonathan Rochford

doi:10.1021/acs.organomet.8b00584

Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO ₂ 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 C. Grills, Jonathan Rochford

Brookhaven National Laboratory

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

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..

Original language	English
Pages (from-to)	1317-1329
Number of pages	13
Journal	Organometallics
Volume	38
Issue number	6
DOIs	https://doi.org/10.1021/acs.organomet.8b00584
Publication status	Published - Mar 25 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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McKinnon, M., Ngo, K. T., Sobottka, S., Sarkar, B., Ertem, M. Z., Grills, D. C., & Rochford, J. (2019). Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO ₂ Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes Organometallics, 38(6), 1317-1329. https://doi.org/10.1021/acs.organomet.8b00584

Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO ₂ 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 C.; Rochford, Jonathan.

In: Organometallics, Vol. 38, No. 6, 25.03.2019, p. 1317-1329.

Research output: Contribution to journal › Article › peer-review

McKinnon, M, Ngo, KT, Sobottka, S, Sarkar, B, Ertem, MZ, Grills, DC & Rochford, J 2019, ' Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO ₂ Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes ', Organometallics, vol. 38, no. 6, pp. 1317-1329. https://doi.org/10.1021/acs.organomet.8b00584

McKinnon M, Ngo KT, Sobottka S, Sarkar B, Ertem MZ, Grills DC et al. Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO ₂ Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes Organometallics. 2019 Mar 25;38(6):1317-1329. https://doi.org/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 CO ₂ Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes In: Organometallics. 2019 ; Vol. 38, No. 6. pp. 1317-1329.

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title = " Synergistic Metal-Ligand Redox Cooperativity for Electrocatalytic CO 2 Reduction Promoted by a Ligand-Based Redox Couple in Mn and Re Tricarbonyl Complexes ",

abstract = " 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.. ",

author = "Meaghan McKinnon and Ngo, {Ken T.} and Sebastian Sobottka and Biprajit Sarkar and Ertem, {Mehmed Z.} and Grills, {David C.} and Jonathan Rochford",

note = "Funding Information: J.R. thanks the National Science Foundation for support under Grant No. CHE-1301132. The work at BNL (D.C.G. and M.Z.E.), including use of the Van de Graaff facility of the BNL Accelerator Center for Energy Research (ACER), was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, under Contract No. DE- SC0012704. K.T.N. is grateful to the DOE for an Office of Science Graduate Student Research (SCGSR) award. Some of this research used resources of the Center for Functional Nanomaterials (CFN) for the fabrication of optics for PR-TRIR experiments and computational modeling studies. The CFN is a U.S. DOE Office of Science Facility at Brookhaven National Laboratory, operating under Contract No. DESC0012704.",

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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

N1 - Funding Information: J.R. thanks the National Science Foundation for support under Grant No. CHE-1301132. The work at BNL (D.C.G. and M.Z.E.), including use of the Van de Graaff facility of the BNL Accelerator Center for Energy Research (ACER), was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, under Contract No. DE- SC0012704. K.T.N. is grateful to the DOE for an Office of Science Graduate Student Research (SCGSR) award. Some of this research used resources of the Center for Functional Nanomaterials (CFN) for the fabrication of optics for PR-TRIR experiments and computational modeling studies. The CFN is a U.S. DOE Office of Science Facility at Brookhaven National Laboratory, operating under Contract No. DESC0012704.

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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