Turning on the protonation-first pathway for electrocatalytic CO2 reduction by manganese bipyridyl tricarbonyl complexes

Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani; Narayanan, Remya; Grills, David C.; Ertem, Mehmed Z.; Rochford, Jonathan

doi:10.1021/jacs.6b08776

Title: Turning on the protonation-first pathway for electrocatalytic CO₂ reduction by manganese bipyridyl tricarbonyl complexes

Journal Article · Tue Jan 24 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b08776· OSTI ID:1345736

Ngo, Ken T. ^[1]; McKinnon, Meaghan ^[1]; Mahanti, Bani ^[1]; Narayanan, Remya ^[1];

^[2]; Ertem, Mehmed Z. ^[2];

^[1]

Univ. of Massachusetts, Boston, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Electrocatalytic reduction of CO₂ to CO is reported for the complex, {fac-Mn^I([(MeO)₂Ph]₂bpy)(CO)₃(CH₃CN)}(OTf), containing four pendant methoxy groups, where [(MeO)₂Ph]₂bpy = 6,6'-bis(2,6-dimethoxyphenyl)-2,2'-bipyridine. In addition to a steric influence similar to that previously established for the 6,6'-dimesityl-2,2'-bipyridine ligand in [fac-MnI(mes₂bpy)(CO)₃(CH₃CN)](OTf), which prevents Mn⁰–Mn⁰ dimerization, the [(MeO)₂Ph]₂bpy ligand introduces an additional electronic influence combined with a weak allosteric hydrogen-bonding interaction that significantly lowers the activation barrier for C–OH bond cleavage from the metallocarboxylic acid intermediate. This provides access to the thus far elusive protonation-first pathway, minimizing the required overpotential for electrocatalytic CO₂ to CO conversion by Mn(I) polypyridyl catalysts, while concurrently maintaining a respectable turnover frequency. Comprehensive electrochemical and computational studies here confirm the positive influence of the [(MeO)₂Ph]₂bpy ligand framework on electrocatalytic CO₂ reduction and its dependence upon the concentration and pK_a of the external Bronsted acid proton source (water, methanol, trifluoroethanol, and phenol) that is required for this class of manganese catalyst. Linear sweep voltammetry studies show that both phenol and trifluoroethanol as proton sources exhibit the largest protonation-first catalytic currents in combination with {fac-Mn^I([(MeO)₂Ph]₂bpy)(CO)₃(CH₃CN)}(OTf), saving up to 0.55 V in overpotential with respect to the thermodynamically demanding reduction-first pathway, while bulk electrolysis studies confirm a high product selectivity for CO formation. As a result, to gain further insight into catalyst activation, time-resolved infrared (TRIR) spectroscopy combined with pulse-radiolysis (PR-TRIR), infrared spectroelectrochemistry, and density functional theory calculations were used to establish the v(CO) stretching frequencies and energetics of key redox intermediates relevant to catalyst activation.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704

OSTI ID:: 1345736

Report Number(s):: BNL-113576-2017-JA; R&D Project: CO026

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 7; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 185 works

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References (93)

Energy Demand and Climate Change Cocks, Franklin Hadley Wiley‐VCH Verlag GmbH & Co https://doi.org/10.1002/9783527627035	book	January 2009
Development of Novel Catalysts for Fischer-Tropsch Synthesis: Tuning the Product Selectivity Zhang, Qinghong; Kang, Jincan; Wang, Ye ChemCatChem, Vol. 2, Issue 9 https://doi.org/10.1002/cctc.201000071	journal	July 2010
Thermodynamic Aspects of Electrocatalytic CO ₂ Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte Matsubara, Yasuo; Grills, David C.; Kuwahara, Yutaka ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b00656	journal	October 2015
Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities Arakawa, Hironori; Aresta, Michele; Armor, John N. Chemical Reviews, Vol. 101, Issue 4 https://doi.org/10.1021/cr000018s	journal	April 2001
A Local Proton Source Enhances CO ₂ Electroreduction to CO by a Molecular Fe Catalyst Costentin, Cyrille; Drouet, Samuel; Robert, Marc Science, Vol. 338, Issue 6103 https://doi.org/10.1126/science.1224581	journal	October 2012
Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J. Inorganic Chemistry, Vol. 54, Issue 24 https://doi.org/10.1021/acs.inorgchem.5b02136	journal	December 2015
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels Qiao, Jinli; Liu, Yuyu; Hong, Feng Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60323G	journal	January 2014
The coordination chemistry of carbon dioxide and its relevance for catalysis: a critical survey Leitner, W. Coordination Chemistry Reviews, Vol. 153 https://doi.org/10.1016/0010-8545(95)01226-5	journal	August 1996
Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt Fisher, Barbara J.; Eisenberg, Richard Journal of the American Chemical Society, Vol. 102, Issue 24, p. 7361-7363 https://doi.org/10.1021/ja00544a035	journal	September 1980
Electrocatalytic reduction of carbon dioxide by nickel cyclam2+ in water: study of the factors affecting the efficiency and the selectivity of the process Beley, Marc.; Collin, Jean Paul.; Ruppert, Romain. Journal of the American Chemical Society, Vol. 108, Issue 24 https://doi.org/10.1021/ja00284a003	journal	November 1986
Nickel(ii) macrocycles: highly efficient electrocatalysts for the selective reduction of CO2 to CO Schneider, Jacob; Jia, Hongfei; Kobiro, Kazuya Energy & Environmental Science, Vol. 5, Issue 11 https://doi.org/10.1039/c2ee22528j	journal	January 2012
Thermodynamics and kinetics of CO2, CO, and H+ binding to the metal centre of CO2reductioncatalysts Schneider, Jacob; Jia, Hongfei; Muckerman, James T. Chem. Soc. Rev., Vol. 41, Issue 6 https://doi.org/10.1039/C1CS15278E	journal	January 2012
Studies of Cobalt-Mediated Electrocatalytic CO ₂ Reduction Using a Redox-Active Ligand Lacy, David C.; McCrory, Charles C. L.; Peters, Jonas C. Inorganic Chemistry, Vol. 53, Issue 10 https://doi.org/10.1021/ic403122j	journal	April 2014
Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO ₂ with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center Chen, Lingjing; Guo, Zhenguo; Wei, Xi-Guang Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b06535	journal	August 2015
A review of iron and cobalt porphyrins, phthalocyanines and related complexes for electrochemical and photochemical reduction of carbon dioxide Manbeck, Gerald F.; Fujita, Etsuko Journal of Porphyrins and Phthalocyanines, Vol. 19, Issue 01-03 https://doi.org/10.1142/S1088424615300013	journal	January 2015
Current Issues in Molecular Catalysis Illustrated by Iron Porphyrins as Catalysts of the CO ₂ -to-CO Electrochemical Conversion Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel Accounts of Chemical Research, Vol. 48, Issue 12 https://doi.org/10.1021/acs.accounts.5b00262	journal	November 2015
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO ₂ reduction in water Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao Science, Vol. 349, Issue 6253 https://doi.org/10.1126/science.aac8343	journal	August 2015
Turning it off! Disfavouring hydrogen evolution to enhance selectivity for CO production during homogeneous CO ₂ reduction by cobalt–terpyridine complexes Elgrishi, Noémie; Chambers, Matthew B.; Fontecave, Marc Chemical Science, Vol. 6, Issue 4 https://doi.org/10.1039/C4SC03766A	journal	January 2015
Proton-Assisted Reduction of CO ₂ by Cobalt Aminopyridine Macrocycles Chapovetsky, Alon; Do, Thomas H.; Haiges, Ralf Journal of the American Chemical Society, Vol. 138, Issue 18 https://doi.org/10.1021/jacs.6b01980	journal	April 2016
Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO) ₃ Cl (bipy = 2,2′-bipyridine) Hawecker, Jeannot; Lehn, Jean-Marie; Ziessel, Raymond J. Chem. Soc., Chem. Commun., Issue 6 https://doi.org/10.1039/C39840000328	journal	January 1984
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO ₂ Reduction by fac -Re(bpy)(CO) ₃ Cl Keith, John A.; Grice, Kyle A.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja406456g	journal	October 2013
Push or Pull? Proton Responsive Ligand Effects in Rhenium Tricarbonyl CO ₂ Reduction Catalysts Manbeck, Gerald F.; Muckerman, James T.; Szalda, David J. The Journal of Physical Chemistry B, Vol. 119, Issue 24 https://doi.org/10.1021/jp511131x	journal	December 2014
Photo- and Electrocatalytic Reduction of CO ₂ by [Re(CO) ₃ {α,α′-Diimine-(4-piperidinyl-1,8-naphthalimide)}Cl] Complexes Franco, Federico; Cometto, Claudio; Garino, Claudio European Journal of Inorganic Chemistry, Vol. 2015, Issue 2 https://doi.org/10.1002/ejic.201402912	journal	December 2014
Electrochemical CO2 reduction catalyzed by ruthenium complexes [Ru(bpy)2(CO)2]2+ and [Ru(bpy)2(CO)Cl]+. Effect of pH on the formation of CO and HCOO- Ishida, Hitoshi.; Tanaka, Koji.; Tanaka, Toshio. Organometallics, Vol. 6, Issue 1 https://doi.org/10.1021/om00144a033	journal	January 1987
Carbon-Carbon Bond Formation in the Electrochemical Reduction of Carbon Dioxide Catalyzed by a Ruthenium Complex Nagao, Hirotaka; Mizukawa, Tetsunori; Tanaka, Koji Inorganic Chemistry, Vol. 33, Issue 15 https://doi.org/10.1021/ic00093a033	journal	July 1994
Multi-electron reduction of CO2 via RuCO2, C(O)OH, CO, CHO, and CH2OH species Tanaka, Koji; Ooyama, Dai Coordination Chemistry Reviews, Vol. 226, Issue 1-2 https://doi.org/10.1016/S0010-8545(01)00434-9	journal	March 2002
Electrocatalytic reduction of CO2 to CO by polypyridyl ruthenium complexes Chen, Zuofeng; Chen, Chuncheng; Weinberg, David R. Chemical Communications, Vol. 47, Issue 47 https://doi.org/10.1039/c1cc15071e	journal	January 2011
Activating a Low Overpotential CO ₂ Reduction Mechanism by a Strategic Ligand Modification on a Ruthenium Polypyridyl Catalyst Johnson, Ben A.; Maji, Somnath; Agarwala, Hemlata Angewandte Chemie International Edition, Vol. 55, Issue 5 https://doi.org/10.1002/anie.201508490	journal	December 2015
Electrocatalytic reduction of carbon dioxide based on 2,2'-bipyridyl complexes of osmium Bruce, Mitchell R. M.; Megehee, Elise; Sullivan, B. Patrick Inorganic Chemistry, Vol. 31, Issue 23 https://doi.org/10.1021/ic00049a027	journal	November 1992
Electrocatalytic reduction of carbon dioxide by 2,2'-bipyridine complexes of rhodium and iridium Bolinger, C. Mark; Story, Nicole; Sullivan, B. Patrick Inorganic Chemistry, Vol. 27, Issue 25 https://doi.org/10.1021/ic00298a016	journal	December 1988
Electrocatalytic Carbon Dioxide Reduction by Using Cationic Pentamethylcyclopentadienyl-Iridium Complexes with Unsymmetrically Substituted Bipyridine Ligands Sypaseuth, Fanni D.; Matlachowski, Corinna; Weber, Manuela Chemistry - A European Journal, Vol. 21, Issue 17 https://doi.org/10.1002/chem.201404367	journal	March 2015
Electrocatalytic Reduction of Carbon Dioxide by the Binuclear Copper Complex [Cu2(6-(diphenylphosphino-2,2'-bipyridyl)2(MeCN)2][PF6]2 Haines, Raymond J.; Wittrig, Rebecca E.; Kubiak, Clifford P. Inorganic Chemistry, Vol. 33, Issue 21 https://doi.org/10.1021/ic00099a024	journal	October 1994
Carbon dioxide chemistry and electrochemistry of a binuclear cradle complex of nickel(0), Ni2(.mu.-CNMe)(CNMe)2(PPh2CH2PPh2)2 DeLaet, Dru L.; Del Rosario, Renato; Fanwick, Phillip E. Journal of the American Chemical Society, Vol. 109, Issue 3 https://doi.org/10.1021/ja00237a020	journal	February 1987
Electrochemical reduction of carbon dioxide catalyzed by Rh(diphos)2Cl Slater, Sydney; Wagenknecht, John H. Journal of the American Chemical Society, Vol. 106, Issue 18 https://doi.org/10.1021/ja00330a064	journal	September 1984
Electrochemical Reduction of CO₂ to CO Catalyzed by a Bimetallic Palladium Complex Raebiger, James W.; Turner, Jeffrey W.; Noll, Bruce C. Organometallics, Vol. 25, Issue 14, p. 3345-3351 https://doi.org/10.1021/om060228g	journal	July 2006
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001679	journal	December 2009
Electrocatalytic and homogeneous approaches to conversion of CO ₂ to liquid fuels Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B804323J	journal	January 2009
Toward more efficient photochemical CO2 reduction: Use of scCO2 or photogenerated hydrides Doherty, Mark D.; Grills, David C.; Muckerman, James T. Coordination Chemistry Reviews, Vol. 254, Issue 21-22 https://doi.org/10.1016/j.ccr.2009.12.013	journal	November 2010
Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies Takeda, Hiroyuki; Ishitani, Osamu Coordination Chemistry Reviews, Vol. 254, Issue 3-4 https://doi.org/10.1016/j.ccr.2009.09.030	journal	February 2010
The teraton challenge. A review of fixation and transformation of carbon dioxide Mikkelsen, Mette; Jørgensen, Mikkel; Krebs, Frederik C. Energy Environ. Sci., Vol. 3, Issue 1 https://doi.org/10.1039/B912904A	journal	January 2010
Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2?-Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts Hawecker, Jeannot; Lehn, Jean-Marie; Ziessel, Raymond Helvetica Chimica Acta, Vol. 69, Issue 8 https://doi.org/10.1002/hlca.19860690824	journal	December 1986
New Directions for the Photocatalytic Reduction of CO ₂ : Supramolecular, scCO ₂ or Biphasic Ionic Liquid−scCO ₂ Systems Grills, David C.; Fujita, Etsuko The Journal of Physical Chemistry Letters, Vol. 1, Issue 18 https://doi.org/10.1021/jz1010237	journal	September 2010
[Mn(bipyridyl)(CO)3Br]: An Abundant Metal Carbonyl Complex as Efficient Electrocatalyst for CO2 Reduction Bourrez, Marc; Molton, Florian; Chardon-Noblat, Sylvie Angewandte Chemie International Edition, Vol. 50, Issue 42 https://doi.org/10.1002/anie.201103616	journal	September 2011
Manganese as a Substitute for Rhenium in CO ₂ Reduction Catalysts: The Importance of Acids Smieja, Jonathan M.; Sampson, Matthew D.; Grice, Kyle A. Inorganic Chemistry, Vol. 52, Issue 5 https://doi.org/10.1021/ic302391u	journal	February 2013
Mechanism of the Formation of a Mn-Based CO ₂ Reduction Catalyst Revealed by Pulse Radiolysis with Time-Resolved Infrared Detection Grills, David C.; Farrington, Jaime A.; Layne, Bobby H. Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja501051s	journal	April 2014
A local proton source in a [Mn(bpy-R)(CO) ₃ Br]-type redox catalyst enables CO ₂ reduction even in the absence of Brønsted acids Franco, Federico; Cometto, Claudio; Ferrero Vallana, Federico Chem. Commun., Vol. 50, Issue 93 https://doi.org/10.1039/C4CC05563B	journal	January 2014
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A. Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja501252f	journal	February 2014
Mechanistic Contrasts between Manganese and Rhenium Bipyridine Electrocatalysts for the Reduction of Carbon Dioxide Riplinger, Christoph; Sampson, Matthew D.; Ritzmann, Andrew M. Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja508192y	journal	November 2014
Photocatalytic CO ₂ reduction using a Mn complex as a catalyst Takeda, Hiroyuki; Koizumi, Hiroki; Okamoto, Kouhei Chem. Commun., Vol. 50, Issue 12 https://doi.org/10.1039/C3CC48122K	journal	January 2014
Pulsed-EPR Evidence of a Manganese(II) Hydroxycarbonyl Intermediate in the Electrocatalytic Reduction of Carbon Dioxide by a Manganese Bipyridyl Derivative Bourrez, Marc; Orio, Maylis; Molton, Florian Angewandte Chemie International Edition, Vol. 53, Issue 1 https://doi.org/10.1002/anie.201306750	journal	November 2013
NHC-Containing Manganese(I) Electrocatalysts for the Two-Electron Reduction of CO ₂ Agarwal, Jay; Shaw, Travis W.; Stanton, Charles J. Angewandte Chemie International Edition https://doi.org/10.1002/anie.201311099	journal	April 2014
Electrocatalytic Reduction of Carbon Dioxide with a Manganese(I) Tricarbonyl Complex Containing a Nonaromatic α-Diimine Ligand Zeng, Qiang; Tory, Joanne; Hartl, František Organometallics, Vol. 33, Issue 18 https://doi.org/10.1021/om500389y	journal	May 2014
Improving the efficiency of electrochemical CO ₂ reduction using immobilized manganese complexes Walsh, James J.; Smith, Charlotte L.; Neri, Gaia Faraday Discussions, Vol. 183 https://doi.org/10.1039/C5FD00071H	journal	January 2015
Electrocatalytic Reduction of Carbon Dioxide by Mn(CN)(2,2′-bipyridine)(CO) ₃ : CN Coordination Alters Mechanism Machan, Charles W.; Stanton, Charles J.; Vandezande, Jonathon E. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01715	journal	August 2015
Influence of Weak Brønsted Acids on Electrocatalytic CO ₂ Reduction by Manganese and Rhenium Bipyridine Catalysts Riplinger, Christoph; Carter, Emily A. ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501687n	journal	January 2015
A Mn Bipyrimidine Catalyst Predicted To Reduce CO ₂ at Lower Overpotential Lam, Yan Choi; Nielsen, Robert J.; Gray, Harry B. ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/cs501963v	journal	March 2015
Design of a Catalytic Active Site for Electrochemical CO ₂ Reduction with Mn(I)-Tricarbonyl Species Agarwal, Jay; Shaw, Travis W.; Schaefer, Henry F. Inorganic Chemistry, Vol. 54, Issue 11 https://doi.org/10.1021/acs.inorgchem.5b00233	journal	May 2015
Manganese Electrocatalysts with Bulky Bipyridine Ligands: Utilizing Lewis Acids To Promote Carbon Dioxide Reduction at Low Overpotentials Sampson, Matthew D.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 138, Issue 4 https://doi.org/10.1021/jacs.5b12215	journal	January 2016
Electrocatalytic reduction of CO ₂ using Mn complexes with unconventional coordination environments Rao, Gyandshwar Kumar; Pell, Wendy; Korobkov, Ilia Chemical Communications, Vol. 52, Issue 51 https://doi.org/10.1039/C6CC03827A	journal	January 2016
N-Heterocylic Carbene-Based Mn Electrocatalyst for Two-Electron CO ₂ Reduction over Proton Reduction Rawat, Kuber Singh; Mahata, Arup; Choudhuri, Indrani The Journal of Physical Chemistry C, Vol. 120, Issue 16 https://doi.org/10.1021/acs.jpcc.6b02209	journal	April 2016
Chemical catalysis of electrochemical reactions. Homogeneous catalysis of the electrochemical reduction of carbon dioxide by iron("0") porphyrins. Role of the addition of magnesium cations Hammouche, Mohamed; Lexa, Doris; Momenteau, Michel Journal of the American Chemical Society, Vol. 113, Issue 22 https://doi.org/10.1021/ja00022a038	journal	October 1991
Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins. Synergistic Effect of Lewis Acid Cations Bhugun, Iqbal; Lexa, Doris; Savéant, Jean-Michel The Journal of Physical Chemistry, Vol. 100, Issue 51 https://doi.org/10.1021/jp9618486	journal	January 1996
Characterization of Ru(bpy)2(CO)(COO) prepared by CO2 addition to Ru(bpy)2(CO) in acetonitrile Fujita, Etsuko; Chou, Mei; Tanaka, Koji Applied Organometallic Chemistry, Vol. 14, Issue 12 https://doi.org/10.1002/1099-0739(200012)14:12<844::AID-AOC76>3.0.CO;2-G	journal	January 2000
Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins: Synergystic Effect of Weak Brönsted Acids Bhugun, Iqbal; Lexa, Doris; Savéant, Jean-Michel Journal of the American Chemical Society, Vol. 118, Issue 7 https://doi.org/10.1021/ja9534462	journal	January 1996
Ultraefficient homogeneous catalyst for the CO ₂ -to-CO electrochemical conversion Costentin, Cyrille; Passard, Guillaume; Robert, Marc Proceedings of the National Academy of Sciences, Vol. 111, Issue 42 https://doi.org/10.1073/pnas.1416697111	journal	October 2014
Geometrical and electronic structures of the acetyl complex Re(bpy)(CO)3(COCH3) and of [M(bpy)(CO)4](OTf), M=Mn,Re Scheiring, Thomas; Kaim, Wolfgang; Fiedler, Jan Journal of Organometallic Chemistry, Vol. 598, Issue 1 https://doi.org/10.1016/S0022-328X(99)00691-9	journal	March 2000
The Nitrosyl Ligand and the Rhenium−Triflate Bond in Rhenium(I) Complexes Veghini, Dario; Berke, Heinz Inorganic Chemistry, Vol. 35, Issue 16 https://doi.org/10.1021/ic9510829	journal	January 1996
Application of Time-Resolved Infrared Spectroscopy to Electronic Structure in Metal-to-Ligand Charge-Transfer Excited States Dattelbaum, Dana M.; Omberg, Kristin M.; Schoonover, Jon R. Inorganic Chemistry, Vol. 41, Issue 23 https://doi.org/10.1021/ic020400i	journal	November 2002
Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry Rountree, Eric S.; McCarthy, Brian D.; Eisenhart, Thomas T. Inorganic Chemistry, Vol. 53, Issue 19 https://doi.org/10.1021/ic500658x	journal	September 2014
Benchmarking of Homogeneous Electrocatalysts: Overpotential, Turnover Frequency, Limiting Turnover Number Costentin, Cyrille; Passard, Guillaume; Savéant, Jean-Michel Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/jacs.5b00914	journal	April 2015
Catalysis of the electrochemical reduction of carbon dioxide Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel Chem. Soc. Rev., Vol. 42, Issue 6 https://doi.org/10.1039/C2CS35360A	journal	January 2013
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242 https://doi.org/10.1021/ja303560c	journal	June 2012
Molecular Catalysis of Electrochemical Reactions. Mechanistic Aspects Savéant, Jean-Michel Chemical Reviews, Vol. 108, Issue 7, p. 2348-2378 https://doi.org/10.1021/cr068079z	journal	July 2008
Homogeneous redox catalysis of electrochemical reaction Savéant, J. M.; Su, K. B. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 171, Issue 1-2 https://doi.org/10.1016/0022-0728(84)80125-4	journal	August 1984
Qualitative extension of the EC′ Zone Diagram to a molecular catalyst for a multi-electron, multi-substrate electrochemical reaction Martin, Daniel J.; McCarthy, Brian D.; Rountree, Eric S. Dalton Transactions, Vol. 45, Issue 24 https://doi.org/10.1039/C6DT00302H	journal	January 2016
Electrocatalytic CO ₂ Reduction with a Homogeneous Catalyst in Ionic Liquid: High Catalytic Activity at Low Overpotential Grills, David C.; Matsubara, Yasuo; Kuwahara, Yutaka The Journal of Physical Chemistry Letters, Vol. 5, Issue 11 https://doi.org/10.1021/jz500759x	journal	May 2014
Homogeneous redox catalysis of electrochemical reactions Andrieux, C. P.; Blocman, C.; Dumas-Bouchiat, J. M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 113, Issue 1 https://doi.org/10.1016/S0022-0728(80)80508-0	journal	October 1980
Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts Costentin, Cyrille; Savéant, Jean-Michel ChemElectroChem, Vol. 1, Issue 7 https://doi.org/10.1002/celc.201300263	journal	June 2014
Acidities of water and simple alcohols in dimethyl sulfoxide solution Olmstead, William N.; Margolin, Zafra; Bordwell, Frederick G. The Journal of Organic Chemistry, Vol. 45, Issue 16 https://doi.org/10.1021/jo01304a032	journal	August 1980
Equilibrium acidities in dimethyl sulfoxide solution Bordwell, Frederick G. Accounts of Chemical Research, Vol. 21, Issue 12 https://doi.org/10.1021/ar00156a004	journal	December 1988
Acidities and hydrogen bonding of phenols in dimethyl sulfoxide Bordwell, Frederick G.; McCallum, Robert J.; Olmstead, William N. The Journal of Organic Chemistry, Vol. 49, Issue 8 https://doi.org/10.1021/jo00182a020	journal	April 1984
Acidities of strong neutral Brønsted acids in different media: ACIDITIES OF STRONG NEUTRAL BRØNSTED ACIDS Raamat, Elin; Kaupmees, Karl; Ovsjannikov, Gea Journal of Physical Organic Chemistry, Vol. 26, Issue 2 https://doi.org/10.1002/poc.2946	journal	May 2012
Electrocatalytic Reduction of CO ₂ to CO With Re-Pyridyl-NHCs: Proton Source Influence on Rates and Product Selectivities Liyanage, Nalaka P.; Dulaney, Hunter A.; Huckaba, Aron J. Inorganic Chemistry, Vol. 55, Issue 12 https://doi.org/10.1021/acs.inorgchem.6b00626	journal	June 2016
Electrocatalytic CO ₂ reduction with a membrane supported manganese catalyst in aqueous solution Walsh, James J.; Neri, Gaia; Smith, Charlotte L. Chem. Commun., Vol. 50, Issue 84 https://doi.org/10.1039/C4CC06404F	journal	January 2014
Determining the Overpotential for a Molecular Electrocatalyst Appel, Aaron M.; Helm, Monte L. ACS Catalysis, Vol. 4, Issue 2 https://doi.org/10.1021/cs401013v	journal	December 2013
A Comprehensive Self-Consistent Spectrophotometric Acidity Scale of Neutral Brønsted Acids in Acetonitrile Kütt, Agnes; Leito, Ivo; Kaljurand, Ivari The Journal of Organic Chemistry, Vol. 71, Issue 7 https://doi.org/10.1021/jo060031y	journal	March 2006
Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility Grills, David C.; Farrington, Jaime A.; Layne, Bobby H. Review of Scientific Instruments, Vol. 86, Issue 4 https://doi.org/10.1063/1.4918728	journal	April 2015
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Quantitative Classification of Covalent and Noncovalent H-Bonds Grabowski, Sławomir J.; Sokalski, W. Andrzej; Dyguda, Edyta The Journal of Physical Chemistry B, Vol. 110, Issue 13 https://doi.org/10.1021/jp0600817	journal	April 2006
Natural triple excitations in local coupled cluster calculations with pair natural orbitals Riplinger, Christoph; Sandhoefer, Barbara; Hansen, Andreas The Journal of Chemical Physics, Vol. 139, Issue 13 https://doi.org/10.1063/1.4821834	journal	October 2013
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H. Organometallics, Vol. 29, Issue 9 https://doi.org/10.1021/om100106e	journal	May 2010
Direct Measurements of Rate Constants and Activation Volumes for the Binding of H ₂ , D ₂ , N ₂ , C ₂ H ₄ , and CH ₃ CN to W(CO) ₃ (PCy ₃ ) ₂ : Theoretical and Experimental Studies with Time-Resolved Step-Scan FTIR and UV−Vis Spectroscopy Grills, David C.; van Eldik, Rudi; Muckerman, James T. Journal of the American Chemical Society, Vol. 128, Issue 49 https://doi.org/10.1021/ja064627e	journal	December 2006

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Transfer Hydrogenation of Carbonyl Groups, Imines and N ‐Heterocycles Catalyzed by Simple, Bipyridine‐Based Mn ^I Complexes Dubey, Abhishek; Rahaman, S. M. Wahidur; Fayzullin, Robert R. ChemCatChem, Vol. 11, Issue 16 https://doi.org/10.1002/cctc.201900358	journal	April 2019
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Rh ^I -Catalyzed P ^III -Directed C−H Bond Alkylation: Design of Multifunctional Phosphines for Carboxylation of Aryl Bromides with Carbon Dioxide Zhang, Zhuan; Roisnel, Thierry; Dixneuf, Pierre H. Angewandte Chemie International Edition, Vol. 58, Issue 40 https://doi.org/10.1002/anie.201906913	journal	August 2019
Assessing the Electrocatalytic Properties of the {CpRh ^III } ²⁺ -Polyoxometalate Derivative [H ₂ PW ₁₁ O ₃₉ {Rh ^III Cp(OH ₂ )}] ^3- towards CO ₂ Reduction: Assessing the Electrocatalytic Properties of the {CpRh ^III } ²⁺ -Polyoxometalate Derivative [H ₂ PW ₁₁ O ₃₉ {Rh ^III Cp(OH ₂ )}] ^3- towards CO ₂ Reduction Girardi, Marcelo; Platzer, Dominique; Griveau, Sophie European Journal of Inorganic Chemistry, Vol. 2019, Issue 3-4 https://doi.org/10.1002/ejic.201800454	journal	July 2018
Elucidating the origins of enhanced CO ₂ reduction in manganese electrocatalysts bearing pendant hydrogen-bond donors Tignor, Steven E.; Shaw, Travis W.; Bocarsly, Andrew B. Dalton Transactions, Vol. 48, Issue 33 https://doi.org/10.1039/c9dt02060h	journal	January 2019
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Rhenium bipyridine catalysts with hydrogen bonding pendant amines for CO ₂ reduction Hellman, Ashley N.; Haiges, Ralf; Marinescu, Smaranda C. Dalton Transactions, Vol. 48, Issue 38 https://doi.org/10.1039/c9dt02689d	journal	January 2019
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A Highly Active N-Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO ₂ Reduction to CO Franco, Federico; Pinto, Mara F.; Royo, Beatriz Angewandte Chemie International Edition, Vol. 57, Issue 17 https://doi.org/10.1002/anie.201800705	journal	March 2018
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Solvent and Ligand Substitution Effects on the Electrocatalytic Reduction of CO ₂ with [Mo(CO) ₄ ( x,x ′-dimethyl-2,2′-bipyridine)] ( x =4-6) Enhanced at a Gold Cathodic Surface Taylor, James O.; Leavey, Roisín D.; Hartl, František ChemElectroChem, Vol. 5, Issue 21 https://doi.org/10.1002/celc.201800879	journal	August 2018
Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO ₂ by Molecular Catalysts Elouarzaki, Kamal; Kannan, Vishvak; Jose, Vishal Advanced Energy Materials, Vol. 9, Issue 24 https://doi.org/10.1002/aenm.201900090	journal	May 2019
A bis ‐Pyrazolate Pincer on Reduced Cr Deoxygenates CO ₂ : Selective Capture of the Derived Oxide by Cr ^II Labrum, Nicholas S.; Chen, Chun‐Hsing; Caulton, Kenneth G. Chemistry – A European Journal, Vol. 25, Issue 33 https://doi.org/10.1002/chem.201901134	journal	April 2019
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Selective formation of formamidines, carbodiimides and formimidates from isocyanide complexes of Mn( i ) mediated by Ag ₂ O Ruiz, Javier; Sol, Daniel; Mateo, María A. Dalton Transactions, Vol. 47, Issue 18 https://doi.org/10.1039/c8dt01200h	journal	January 2018
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Title: Turning on the protonation-first pathway for electrocatalytic CO₂ reduction by manganese bipyridyl tricarbonyl complexes