Changing the Mechanism for CO 2 Hydrogenation Using Solvent‐Dependent Thermodynamics
Abstract
Abstract A critical scientific challenge for utilization of CO 2 is the development of catalyst systems that function in water and use inexpensive and environmentally friendly reagents. We have used thermodynamic insights to predict and demonstrate that the HCo I (dmpe) 2 catalyst system, previously described for use in organic solvents, can hydrogenate CO 2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO 2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water owing to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity.
- Authors:
-
[1];
[1];
[1]
- Catalysis Science Group Pacific Northwest National Laboratory P.O. Box 999 Richland WA 99352 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1402093
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 56 Journal Issue: 47; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Burgess, Samantha A., Appel, Aaron M., Linehan, John C., and Wiedner, Eric S. Changing the Mechanism for CO 2 Hydrogenation Using Solvent‐Dependent Thermodynamics. Germany: N. p., 2017.
Web. doi:10.1002/anie.201709319.
Burgess, Samantha A., Appel, Aaron M., Linehan, John C., & Wiedner, Eric S. Changing the Mechanism for CO 2 Hydrogenation Using Solvent‐Dependent Thermodynamics. Germany. https://doi.org/10.1002/anie.201709319
Burgess, Samantha A., Appel, Aaron M., Linehan, John C., and Wiedner, Eric S. Mon .
"Changing the Mechanism for CO 2 Hydrogenation Using Solvent‐Dependent Thermodynamics". Germany. https://doi.org/10.1002/anie.201709319.
@article{osti_1402093,
title = {Changing the Mechanism for CO 2 Hydrogenation Using Solvent‐Dependent Thermodynamics},
author = {Burgess, Samantha A. and Appel, Aaron M. and Linehan, John C. and Wiedner, Eric S.},
abstractNote = {Abstract A critical scientific challenge for utilization of CO 2 is the development of catalyst systems that function in water and use inexpensive and environmentally friendly reagents. We have used thermodynamic insights to predict and demonstrate that the HCo I (dmpe) 2 catalyst system, previously described for use in organic solvents, can hydrogenate CO 2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO 2 from a key dihydride intermediate. The need for a strong organic base was eliminated by performing catalysis in water owing to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity.},
doi = {10.1002/anie.201709319},
journal = {Angewandte Chemie (International Edition)},
number = 47,
volume = 56,
place = {Germany},
year = {Mon Oct 23 00:00:00 EDT 2017},
month = {Mon Oct 23 00:00:00 EDT 2017}
}
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Works referenced in this record:
Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel
journal, January 2016
- Connelly Robinson, Samantha J.; Zall, Christopher M.; Miller, Deanna L.
- Dalton Transactions, Vol. 45, Issue 24
Synthesis and Reactivity of Iron Complexes with a New Pyrazine-Based Pincer Ligand, and Application in Catalytic Low-Pressure Hydrogenation of Carbon Dioxide
journal, April 2015
- Rivada-Wheelaghan, Orestes; Dauth, Alexander; Leitus, Gregory
- Inorganic Chemistry, Vol. 54, Issue 9
The use of supercritical fluids as solvents for NMR spectroscopy
journal, October 2005
- Yonker, Clement R.; Linehan, John C.
- Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 47, Issue 1-2, p. 95-109
Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes
journal, September 2012
- Matsubara, Yasuo; Fujita, Etsuko; Doherty, Mark D.
- Journal of the American Chemical Society, Vol. 134, Issue 38
Understanding the Relationship Between Kinetics and Thermodynamics in CO 2 Hydrogenation Catalysis
journal, August 2017
- Jeletic, Matthew S.; Hulley, Elliott B.; Helm, Monte L.
- ACS Catalysis, Vol. 7, Issue 9
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
Aqueous hydrogenation of carbon dioxide catalysed by water-soluble ruthenium aqua complexes under acidic conditions
journal, January 2004
- Hayashi, Hideki; Ogo, Seiji; Fukuzumi, Shunichi
- Chemical Communications, Issue 23
Mechanistic Insight through Factors Controlling Effective Hydrogenation of CO 2 Catalyzed by Bioinspired Proton-Responsive Iridium(III) Complexes
journal, April 2013
- Wang, Wan-Hui; Muckerman, James T.; Fujita, Etsuko
- ACS Catalysis, Vol. 3, Issue 5
A Cobalt-Based Catalyst for the Hydrogenation of CO 2 under Ambient Conditions
journal, July 2013
- Jeletic, Matthew S.; Mock, Michael T.; Appel, Aaron M.
- Journal of the American Chemical Society, Vol. 135, Issue 31
Catalytic Hydrogenation of Carbon Dioxide Using Ir(III)−Pincer Complexes
journal, October 2009
- Tanaka, Ryo; Yamashita, Makoto; Nozaki, Kyoko
- Journal of the American Chemical Society, Vol. 131, Issue 40
Hydrogenation of carbon dioxide to formic acid using water-soluble rhodium catalyststs
journal, January 1993
- Gassner, Franz; Leitner, Walter
- Journal of the Chemical Society, Chemical Communications, Issue 19
Insertion of CO 2 , CS 2 , and COS into Iron(II)−Hydride Bonds
journal, December 2000
- Field, Leslie D.; Lawrenz, Eric T.; Shaw, Warren J.
- Inorganic Chemistry, Vol. 39, Issue 25
Some New Hydrides of Iron and Osmium
journal, July 1960
- Chatt, J.; Hart, F. A.; Hayter, R. G.
- Nature, Vol. 187, Issue 4731
Catalysis for the Valorization of Exhaust Carbon: from CO 2 to Chemicals, Materials, and Fuels. Technological Use of CO 2
journal, November 2013
- Aresta, Michele; Dibenedetto, Angela; Angelini, Antonella
- Chemical Reviews, Vol. 114, Issue 3
p K a Measurements of P(RNCH 2 CH 3 ) 3 N
journal, August 2000
- Kisanga, Philip B.; Verkade, John G.; Schwesinger, Reinhard
- The Journal of Organic Chemistry, Vol. 65, Issue 17
Free formic acid by hydrogenation of carbon dioxide in sodium formate solutions
journal, October 2011
- Zhao, Guoying; Joó, Ferenc
- Catalysis Communications, Vol. 14, Issue 1
Cp*Co(III) Catalysts with Proton-Responsive Ligands for Carbon Dioxide Hydrogenation in Aqueous Media
journal, October 2013
- Badiei, Yosra M.; Wang, Wan-Hui; Hull, Jonathan F.
- Inorganic Chemistry, Vol. 52, Issue 21
Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes
journal, March 2016
- Morris, Robert H.
- Chemical Reviews, Vol. 116, Issue 15
Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry
journal, May 2016
- Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem
- Angewandte Chemie International Edition, Vol. 55, Issue 26
CO 2 reduction or HCO 2 − oxidation? Solvent-dependent thermochemistry of a nickel hydride complex
journal, January 2017
- Ceballos, Bianca M.; Tsay, Charlene; Yang, Jenny Y.
- Chemical Communications, Vol. 53, Issue 53
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO 2 Reduction Catalyst
journal, June 2011
- Schmeier, Timothy J.; Dobereiner, Graham E.; Crabtree, Robert H.
- Journal of the American Chemical Society, Vol. 133, Issue 24
Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX 3 Compounds
journal, December 2011
- Mock, Michael T.; Potter, Robert G.; O’Hagan, Molly J.
- Inorganic Chemistry, Vol. 50, Issue 23
CO 2 Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO 2 Reduction
journal, August 2015
- Wang, Wan-Hui; Himeda, Yuichiro; Muckerman, James T.
- Chemical Reviews, Vol. 115, Issue 23
Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature
journal, September 2016
- Sordakis, Katerina; Tsurusaki, Akihiro; Iguchi, Masayuki
- Chemistry - A European Journal, Vol. 22, Issue 44
Thermodynamic Hydricity of Transition Metal Hydrides
journal, June 2016
- Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.
- Chemical Reviews, Vol. 116, Issue 15
Hydrogenation of CO 2 in Water Using a Bis(diphosphine) Ni–H Complex
journal, March 2017
- Burgess, Samantha A.; Kendall, Alexander J.; Tyler, David R.
- ACS Catalysis, Vol. 7, Issue 4
Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures
journal, March 2012
- Hull, Jonathan F.; Himeda, Yuichiro; Wang, Wan-Hui
- Nature Chemistry, Vol. 4, Issue 5, p. 383-388
A Cobalt Hydride Catalyst for the Hydrogenation of CO 2 : Pathways for Catalysis and Deactivation
journal, September 2014
- Jeletic, Matthew S.; Helm, Monte L.; Hulley, Elliott B.
- ACS Catalysis, Vol. 4, Issue 10
Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium
journal, February 2016
- Pitman, Catherine L.; Brereton, Kelsey R.; Miller, Alexander J. M.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Ab Initio Calculations of Thermodynamic Hydricities of Transition-Metal Hydrides in Acetonitrile
journal, August 2007
- Qi, Xiu-Juan; Fu, Yao; Liu, Lei
- Organometallics, Vol. 26, Issue 17
Mechanistic investigation of CO2 hydrogenation by Ru(ii) and Ir(iii) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step
journal, January 2006
- Ogo, Seiji; Kabe, Ryota; Hayashi, Hideki
- Dalton Transactions, Issue 39
Low-Pressure Hydrogenation of Carbon Dioxide Catalyzed by an Iron Pincer Complex Exhibiting Noble Metal Activity
journal, September 2011
- Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory
- Angewandte Chemie, Vol. 123, Issue 42
Transformation of Carbon Dioxide
journal, June 2007
- Sakakura, Toshiyasu; Choi, Jun-Chul; Yasuda, Hiroyuki
- Chemical Reviews, Vol. 107, Issue 6
Low-Pressure Hydrogenation of Carbon Dioxide Catalyzed by an Iron Pincer Complex Exhibiting Noble Metal Activity
journal, September 2011
- Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory
- Angewandte Chemie International Edition, Vol. 50, Issue 42
Catalytic thermal carbon-hydrogen activation with manganese complexes: evidence for .eta.2-H2 coordination in a neutral manganese complex and its role in carbon-hydrogen activation
journal, November 1992
- Perthuisot, Christophe; Fan, Mingxin; Jones, William D.
- Organometallics, Vol. 11, Issue 11
Anthropogenic Chemical Carbon Cycle for a Sustainable Future
journal, August 2011
- Olah, George A.; Prakash, G. K. Surya; Goeppert, Alain
- Journal of the American Chemical Society, Vol. 133, Issue 33
Recent advances in the homogeneous hydrogenation of carbon dioxide
journal, December 2004
- Jessop, Philip G.; Joó, Ferenc; Tai, Chih-Cheng
- Coordination Chemistry Reviews, Vol. 248, Issue 21-24, p. 2425-2442
Formation of molecular hydrogen complexes of iron by the reversible protonation of iron dihydrides with alcohols
journal, January 1988
- Baker, Murray V.; Field, Leslie D.; Young, David J.
- Journal of the Chemical Society, Chemical Communications, Issue 8
CO 2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand
journal, February 2015
- Onishi, Naoya; Xu, Shaoan; Manaka, Yuichi
- Inorganic Chemistry, Vol. 54, Issue 11
Ruthenium-Catalyzed Hydrogenation of Bicarbonate in Water
journal, July 2010
- Federsel, Christopher; Jackstell, Ralf; Boddien, Albert
- ChemSusChem, Vol. 3, Issue 9
Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen
journal, January 2015
- Connelly, Samantha J.; Wiedner, Eric S.; Appel, Aaron M.
- Dalton Transactions, Vol. 44, Issue 13
New Ru( ii ) N′NN′-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO 2 or bicarbonates to formate salts
journal, January 2017
- Dai, Zengjin; Luo, Qi; Cong, Hengjiang
- New Journal of Chemistry, Vol. 41, Issue 8
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013
- Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
- Chemical Reviews, Vol. 113, Issue 8
Ab Initio Calculations of p K a Values of Transition-Metal Hydrides in Acetonitrile
journal, December 2006
- Qi, Xiu-Juan; Liu, Lei; Fu, Yao
- Organometallics, Vol. 25, Issue 25
Selektive katalytische Synthesen mit Kohlendioxid und Wasserstoff: Katalyse-Schach an der Nahtstelle zwischen Energie und Chemie
journal, May 2016
- Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem
- Angewandte Chemie, Vol. 128, Issue 26
Solvation Effects on Transition Metal Hydricity
journal, November 2015
- Tsay, Charlene; Livesay, Brooke N.; Ruelas, Samantha
- Journal of the American Chemical Society, Vol. 137, Issue 44
Investigation of the hydroformylation of ethylene in liquid carbon dioxide
journal, May 2002
- Yonker, Clement R.; Linehan, John C.
- Journal of Organometallic Chemistry, Vol. 650, Issue 1-2