Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–

Carr, Cody R.; Cluff, David B.; Berben, Louise A.

doi:10.1021/acs.organomet.9b00848

Title: Breaking Scaling Relationships in CO₂ Electroreduction with Isoelectronic Analogs [Fe₄N(CO)₁₂]^– and [Fe₃MnO(CO)₁₂]^–

Abstract

[Fe4N(CO)12]-0 and [Fe3MnO(CO)12]- have the same total electron count and overall charge, as well as similar reduction potentials of -1.21 and -1.17 V vs SCE in MeCN, respectively. Both clusters form the reduced hydride upon single electron transfer (ET) and proton transfer (PT). It is known that [Fe4N(CO)12]- is an electrocatalyst for selective CO2 reduction to formate at -1.2 V vs SCE in either pH 7 buffered water or in MeCN/H2O (95:5) and an effective electrocatalyst for H+ reduction to H2 under N2 under the same conditions. In contrast, [Fe3MnO(CO)12]=- affords no products upon electrolysis, beyond [H-Fe3MnO(CO)12]-. We determine that [H-Fe3MnO(CO)12]- is a weaker hydride donor than [H-Fe4N(CO)12]- by about 4 kcal mol–1, and this is a breaking of the hydricity versus reduction potential scaling relationship previously established for a series of metal carbonyl clusters electrocatalysts.

Authors:

Carr, Cody R. ^[1]; Cluff, David B. ^[1];

^[1]

Univ. of California, Davis, CA (United States)

Publication Date:: Mon Mar 02 00:00:00 EST 2020

Research Org.:: Univ. of California, Davis, CA (United States)

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

OSTI Identifier:: 1657669

Alternate Identifier(s):: OSTI ID: 1773842

Grant/Contract Number:: SC0016395

Resource Type:: Accepted Manuscript

Journal Name:: Organometallics

Additional Journal Information:: Journal Volume: 39; Journal Issue: 9; Journal ID: ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 14 SOLAR ENERGY; Redox reactions; Anions; Reaction mechanisms; Electrodes; Catalysts; 25 ENERGY STORAGE; 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; iron; manganese; electrocatalysis; CO2 reduction

Citation Formats


                    Carr, Cody R., Cluff, David B., and Berben, Louise A. Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.organomet.9b00848.

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                    Carr, Cody R., Cluff, David B., & Berben, Louise A. Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–.  United States.  https://doi.org/10.1021/acs.organomet.9b00848

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                    Carr, Cody R., Cluff, David B., and Berben, Louise A. Mon .  
"Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–".  United States.  https://doi.org/10.1021/acs.organomet.9b00848.  https://www.osti.gov/servlets/purl/1657669.

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@article{osti_1657669,

  title        = {Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–},

  author       = {Carr, Cody R. and Cluff, David B. and Berben, Louise A.},

  abstractNote = {[Fe4N(CO)12]-0 and [Fe3MnO(CO)12]- have the same total electron count and overall charge, as well as similar reduction potentials of -1.21 and -1.17 V vs SCE in MeCN, respectively. Both clusters form the reduced hydride upon single electron transfer (ET) and proton transfer (PT). It is known that [Fe4N(CO)12]- is an electrocatalyst for selective CO2 reduction to formate at -1.2 V vs SCE in either pH 7 buffered water or in MeCN/H2O (95:5) and an effective electrocatalyst for H+ reduction to H2 under N2 under the same conditions. In contrast, [Fe3MnO(CO)12]=- affords no products upon electrolysis, beyond [H-Fe3MnO(CO)12]-. We determine that [H-Fe3MnO(CO)12]- is a weaker hydride donor than [H-Fe4N(CO)12]- by about 4 kcal mol–1, and this is a breaking of the hydricity versus reduction potential scaling relationship previously established for a series of metal carbonyl clusters electrocatalysts.},

  doi          = {10.1021/acs.organomet.9b00848},

  journal      = {Organometallics},

  number       = 9,

  volume       = 39,

  place        = {United States},

  year         = {Mon Mar 02 00:00:00 EST 2020},

  month        = {Mon Mar 02 00:00:00 EST 2020}

}

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Works referenced in this record:

A Case for Electrofuels
journal, October 2016

Tatin, Arnaud; Bonin, Julien; Robert, Marc
ACS Energy Letters, Vol. 1, Issue 5
DOI: 10.1021/acsenergylett.6b00510

Research opportunities to advance solar energy utilization
journal, January 2016

Lewis, N. S.
Science, Vol. 351, Issue 6271
DOI: 10.1126/science.aad1920

The Holy Grail: Chemistry Enabling an Economically Viable CO ₂ Capture, Utilization, and Storage Strategy
journal, March 2017

Senftle, Thomas P.; Carter, Emily A.
Accounts of Chemical Research, Vol. 50, Issue 3
DOI: 10.1021/acs.accounts.6b00479

What would it take for renewably powered electrosynthesis to displace petrochemical processes?
journal, April 2019

De Luna, Phil; Hahn, Christopher; Higgins, Drew
Science, Vol. 364, Issue 6438
DOI: 10.1126/science.aav3506

Electrocatalytic and homogeneous approaches to conversion of CO ₂ to liquid fuels
journal, January 2009

Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.
Chem. Soc. Rev., Vol. 38, Issue 1
DOI: 10.1039/B804323J

Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H ₂ Production
journal, March 2018

Klug, Christina M.; Cardenas, Allan Jay P.; Bullock, R. Morris
ACS Catalysis, Vol. 8, Issue 4
DOI: 10.1021/acscatal.7b04379

Identifying and Breaking Scaling Relations in Molecular Catalysis of Electrochemical Reactions
journal, August 2017

Pegis, Michael L.; Wise, Catherine F.; Koronkiewicz, Brian
Journal of the American Chemical Society, Vol. 139, Issue 32
DOI: 10.1021/jacs.7b05642

Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO ₂ -to-CO Electrochemical Conversion
journal, December 2016

Azcarate, Iban; Costentin, Cyrille; Robert, Marc
Journal of the American Chemical Society, Vol. 138, Issue 51
DOI: 10.1021/jacs.6b07014

Renewable Formate from C–H Bond Formation with CO ₂ : Using Iron Carbonyl Clusters as Electrocatalysts
journal, August 2017

Loewen, Natalia D.; Neelakantan, Taruna V.; Berben, Louise A.
Accounts of Chemical Research, Vol. 50, Issue 9
DOI: 10.1021/acs.accounts.7b00302

Utilization of Thermodynamic Scaling Relationships in Hydricity To Develop Nickel Hydrogen Evolution Reaction Electrocatalysts with Weak Acids and Low Overpotentials
journal, September 2018

Ostericher, Andrew L.; Waldie, Kate M.; Kubiak, Clifford P.
ACS Catalysis, Vol. 8, Issue 10
DOI: 10.1021/acscatal.8b02922

Towards an intelligent design of molecular electrocatalysts
journal, October 2017

Costentin, Cyrille; Savéant, Jean-Michel
Nature Reviews Chemistry, Vol. 1, Issue 11
DOI: 10.1038/s41570-017-0087

Electrocatalytic Hydrogen Evolution from Water by a Series of Iron Carbonyl Clusters
journal, October 2013

Nguyen, An D.; Rail, M. Diego; Shanmugam, Maheswaran
Inorganic Chemistry, Vol. 52, Issue 21
DOI: 10.1021/ic4023882

Tailoring Electrocatalysts for Selective CO ₂ or H ⁺ Reduction: Iron Carbonyl Clusters as a Case Study
journal, November 2015

Taheri, Atefeh; Berben, Louise A.
Inorganic Chemistry, Vol. 55, Issue 2
DOI: 10.1021/acs.inorgchem.5b02293

Directing the Reactivity of [HFe ₄ N(CO) ₁₂ ] ⁻ toward H ⁺ or CO ₂ Reduction by Understanding the Electrocatalytic Mechanism
journal, November 2011

Rail, M. Diego; Berben, Louise A.
Journal of the American Chemical Society, Vol. 133, Issue 46
DOI: 10.1021/ja208312t

An Iron Electrocatalyst for Selective Reduction of CO ₂ to Formate in Water: Including Thermochemical Insights
journal, November 2015

Taheri, Atefeh; Thompson, Emily J.; Fettinger, James C.
ACS Catalysis, Vol. 5, Issue 12
DOI: 10.1021/acscatal.5b01708

Synthesis and Structure of[(PPh3)2N][Fe3Mn(CO)12(μ4-O)]: A Butterfly Oxo Cluster
journal, March 1987

Schauer, Cynthia K.; Shriver, Duward F.
Angewandte Chemie International Edition in English, Vol. 26, Issue 3
DOI: 10.1002/anie.198702551

Synthesis, Structure, and Bonding of Butterfly Clusters Containing .mu.4-Oxo and .mu.4-Sulfido Ligands: [(PPh3)2N][Fe3M(CO)12(.mu.4-E)] (E = O, S; M = Mn, Re)
journal, September 1995

Schauer, Cynthia K.; Harris, Suzanne; Sabat, Michal
Inorganic Chemistry, Vol. 34, Issue 20
DOI: 10.1021/ic00124a017

Metal clusters with exposed and low-coordinate nitride nitrogen atoms
journal, October 1980

Tachikawa, M.; Stein, Judith; Muetterties, E. L.
Journal of the American Chemical Society, Vol. 102, Issue 21
DOI: 10.1021/ja00541a084

Metal clusters. 25. A uniquely bonded C-H group and reactivity of a low-coordinate carbidic carbon atom
journal, June 1980

Tachikawa, M.; Muetterties, E. L.
Journal of the American Chemical Society, Vol. 102, Issue 13
DOI: 10.1021/ja00533a051

A closed three-center carbon-hydrogen-metal interaction. A neutron diffraction study of HFe4(.eta.2-CH)(CO)12
journal, March 1981

Beno, M. A.; Williams, Jack M.; Tachikawa, M.
Journal of the American Chemical Society, Vol. 103, Issue 6
DOI: 10.1021/ja00396a032

Proton reactivity of butterfly oxo and sulfido clusters and structural characterization of HFe3Mn(CO)10(dmpm)(μ4-O)
journal, April 2000

Schauer, Cynthia K.; Voss, Eric J.; Sabat, Michal
Inorganica Chimica Acta, Vol. 300-302
DOI: 10.1016/S0020-1693(99)00574-5

Elements of Molecular and Biomolecular Electrochemistry
book, January 2006

Savéant, Jean-Michel
DOI: 10.1002/0471758078

Electrochemical Methods for Assessing Kinetic Factors in the Reduction of CO ₂ to Formate: Implications for Improving Electrocatalyst Design
journal, May 2018

Taheri, Atefeh; Carr, Cody R.; Berben, Louise A.
ACS Catalysis, Vol. 8, Issue 7
DOI: 10.1021/acscatal.8b01799

H ₂ Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation
journal, November 2010

Fourmond, Vincent; Jacques, Pierre-André; Fontecave, Marc
Inorganic Chemistry, Vol. 49, Issue 22
DOI: 10.1021/ic101187v

A pendant proton shuttle on [Fe ₄ N(CO) ₁₂ ] ⁻ alters product selectivity in formate vs. H ₂ production via the hydride [H–Fe ₄ N(CO) ₁₂ ] ⁻
journal, January 2016

Loewen, Natalia D.; Thompson, Emily J.; Kagan, Michael
Chemical Science, Vol. 7, Issue 4
DOI: 10.1039/C5SC03169A

Electrode initiated proton-coupled electron transfer to promote degradation of a nickel( ii ) coordination complex
journal, January 2015

McCarthy, Brian D.; Donley, Carrie L.; Dempsey, Jillian L.
Chemical Science, Vol. 6, Issue 5
DOI: 10.1039/C5SC00476D

Kinetics and mechanism of carbon dioxide insertion into a metal-hydride bond. A large solvent effect and an inverse kinetic isotope effect
journal, July 1986

Sullivan, B. Patrick.; Meyer, Thomas J.
Organometallics, Vol. 5, Issue 7
DOI: 10.1021/om00138a035

Directing the reactivity of metal hydrides for selective CO ₂ reduction
journal, November 2018

Ceballos, Bianca M.; Yang, Jenny Y.
Proceedings of the National Academy of Sciences, Vol. 115, Issue 50
DOI: 10.1073/pnas.1811396115

HRh(dppb) ₂ , a Powerful Hydride Donor
journal, October 2002

Price, Andrew J.; Ciancanelli, Rebecca; Noll, Bruce C.
Organometallics, Vol. 21, Issue 22
DOI: 10.1021/om020421k

Trialkylborane-Assisted CO ₂ Reduction by Late Transition Metal Hydrides
journal, August 2011

Miller, Alexander J. M.; Labinger, Jay A.; Bercaw, John E.
Organometallics, Vol. 30, Issue 16
DOI: 10.1021/om200364w

Simple construction of an infrared optically transparent thin-layer electrochemical cell
journal, November 1991

Krejčik, M.; Daněk, M.; Hartl, F.
Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 317, Issue 1-2
DOI: 10.1016/0022-0728(91)85012-E

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Title: Breaking Scaling Relationships in CO2 Electroreduction with Isoelectronic Analogs [Fe4N(CO)12]– and [Fe3MnO(CO)12]–

Abstract

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Title: Breaking Scaling Relationships in CO₂ Electroreduction with Isoelectronic Analogs [Fe₄N(CO)₁₂]^– and [Fe₃MnO(CO)₁₂]^–

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journal, March 2018

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Synthesis and Structure of[(PPh3)2N][Fe3Mn(CO)12(μ4-O)]: A Butterfly Oxo Cluster
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Metal clusters with exposed and low-coordinate nitride nitrogen atoms
journal, October 1980

Metal clusters. 25. A uniquely bonded C-H group and reactivity of a low-coordinate carbidic carbon atom
journal, June 1980

A closed three-center carbon-hydrogen-metal interaction. A neutron diffraction study of HFe4(.eta.2-CH)(CO)12
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Proton reactivity of butterfly oxo and sulfido clusters and structural characterization of HFe3Mn(CO)10(dmpm)(μ4-O)
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Elements of Molecular and Biomolecular Electrochemistry
book, January 2006

Electrochemical Methods for Assessing Kinetic Factors in the Reduction of CO ₂ to Formate: Implications for Improving Electrocatalyst Design
journal, May 2018

H ₂ Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation
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A pendant proton shuttle on [Fe ₄ N(CO) ₁₂ ] ⁻ alters product selectivity in formate vs. H ₂ production via the hydride [H–Fe ₄ N(CO) ₁₂ ] ⁻
journal, January 2016

Electrode initiated proton-coupled electron transfer to promote degradation of a nickel( ii ) coordination complex
journal, January 2015

Kinetics and mechanism of carbon dioxide insertion into a metal-hydride bond. A large solvent effect and an inverse kinetic isotope effect
journal, July 1986

Directing the reactivity of metal hydrides for selective CO ₂ reduction
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