Additive-Free Formic Acid Dehydrogenation Using a Pincer- Supported Iron Catalyst

Bernskoetter, Wesley; Curley, Julia; Hazari, Nilay

doi:10.1002/cctc.202000066

Additive-Free Formic Acid Dehydrogenation Using a Pincer- Supported Iron Catalyst

Journal Article · Mon Apr 06 00:00:00 EDT 2020 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.202000066· OSTI ID:1594877

^[1]; Curley, Julia ^[2]; ^[2]

Univ. of Missouri, Columbia, MO (United States); University of Missouri
Yale Univ., New Haven, CT (United States)

The iron complex (^iPrPN^MeP)Fe(H)₂(CO) (^iPrPN^MeP = CH₃N(CH₂CH₂PⁱPr₂)₂), which features a pincer ligand with a tertiary amine, can give up to 100,000 turnovers for additive-free formic acid dehydrogenation (FADH). This is two orders of magnitude higher than any previously reported base metal system. Furthermore, mechanistic studies reveal the catalytic reaction pathway and provide guidance for the development of improved catalytic systems for additive-free FADH.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Missouri, Columbia, MO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018222

OSTI ID:: 1594877

Alternate ID(s):: OSTI ID: 1777135
OSTI ID: 1599664

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 7 Vol. 12; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation Catalyzed by Iridium Complexes Bearing Pyridyl-pyrazole Ligands: Effect of an Electron-donating Substituent on the Pyrazole Ring on the Catalytic Activity and Durability Onishi, Naoya; Kanega, Ryoichi; Fujita, Etsuko Advanced Synthesis & Catalysis, Vol. 361, Issue 2 https://doi.org/10.1002/adsc.201801323	journal	November 2018
Chemical and Physical Solutions for Hydrogen Storage Eberle, Ulrich; Felderhoff, Michael; Schüth, Ferdi Angewandte Chemie International Edition, Vol. 48, Issue 36 https://doi.org/10.1002/anie.200806293	journal	August 2009
Well-Defined Bifunctional Iron Catalysts for the Hydrogenation of Ketones: Iron, the New Ruthenium Bauer, Gerald; Kirchner, Karl A. Angewandte Chemie International Edition, Vol. 50, Issue 26 https://doi.org/10.1002/anie.201101579	journal	May 2011
The NH Functional Group in Organometallic Catalysis Zhao, Baoguo; Han, Zhaobin; Ding, Kuiling Angewandte Chemie International Edition, Vol. 52, Issue 18 https://doi.org/10.1002/anie.201204921	journal	March 2013
Metal-Ligand Cooperation Khusnutdinova, Julia R.; Milstein, David Angewandte Chemie International Edition, Vol. 54, Issue 42 https://doi.org/10.1002/anie.201503873	journal	September 2015
Catalytic Dehydrogenation of Formic Acid with Ruthenium‐PNP‐Pincer Complexes: Comparing N‐Methylated and NH‐Ligands Agapova, Anastasiya; Alberico, Elisabetta; Kammer, Anja ChemCatChem, Vol. 11, Issue 7 https://doi.org/10.1002/cctc.201801897	journal	March 2019
Unprecedentedly High Formic Acid Dehydrogenation Activity on an Iridium Complex with an N , N ′-Diimine Ligand in Water Wang, Zhijun; Lu, Sheng-Mei; Li, Jun Chemistry - A European Journal, Vol. 21, Issue 36 https://doi.org/10.1002/chem.201502086	journal	July 2015
Development of an Iridium-Based Catalyst for High-Pressure Evolution of Hydrogen from Formic Acid Iguchi, Masayuki; Himeda, Yuichiro; Manaka, Yuichi ChemSusChem, Vol. 9, Issue 19 https://doi.org/10.1002/cssc.201600697	journal	August 2016
Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N -Heterocyclic Carbene Complexes of Late Transition Metals Jantke, Dominik; Pardatscher, Lorenz; Drees, Markus ChemSusChem, Vol. 9, Issue 19 https://doi.org/10.1002/cssc.201600861	journal	September 2016
Highly Efficient Base-Free Dehydrogenation of Formic Acid at Low Temperature Prichatz, Christoph; Trincado, Monica; Tan, Lilin ChemSusChem, Vol. 11, Issue 18 https://doi.org/10.1002/cssc.201801072	journal	August 2018
Base‐Free Dehydrogenation of Aqueous and Neat Formic Acid with Iridium(III) Cp*(dipyridylamine) Catalysts Wang, Shengdong; Huang, Haiyun; Roisnel, Thierry ChemSusChem, Vol. 12, Issue 1 https://doi.org/10.1002/cssc.201802275	journal	November 2018
A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water: A Precious Catalyst: Rhodium-Catalyzed Formic Acid Dehydrogenation in Water Fink, Cornel; Laurenczy, Gábor European Journal of Inorganic Chemistry, Vol. 2019, Issue 18 https://doi.org/10.1002/ejic.201900344	journal	April 2019
Quantitative aqueous phase formic acid dehydrogenation using iron(II) based catalysts Montandon-Clerc, Mickael; Dalebrook, Andrew F.; Laurenczy, Gábor Journal of Catalysis, Vol. 343 https://doi.org/10.1016/j.jcat.2015.11.012	journal	November 2016
Renewable energy resources: Current status, future prospects and their enabling technology Ellabban, Omar; Abu-Rub, Haitham; Blaabjerg, Frede Renewable and Sustainable Energy Reviews, Vol. 39 https://doi.org/10.1016/j.rser.2014.07.113	journal	November 2014
Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts Bernskoetter, Wesley H.; Hazari, Nilay Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.7b00039	journal	February 2017
CO ₂ Hydrogenation to Formate and Methanol as an Alternative to Photo- and Electrochemical CO ₂ Reduction Wang, Wan-Hui; Himeda, Yuichiro; Muckerman, James T. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00197	journal	August 2015
Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K. Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00182	journal	October 2017
First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands Alig, Lukas; Fritz, Maximilian; Schneider, Sven Chemical Reviews, Vol. 119, Issue 4 https://doi.org/10.1021/acs.chemrev.8b00555	journal	October 2018
Selective Formic Acid Dehydrogenation Catalyzed by Fe-PNP Pincer Complexes Based on the 2,6-Diaminopyridine Scaffold Mellone, Irene; Gorgas, Nikolaus; Bertini, Federica Organometallics, Vol. 35, Issue 19 https://doi.org/10.1021/acs.organomet.6b00551	journal	September 2016
Catalytic Formic Acid Dehydrogenation and CO ₂ Hydrogenation Using Iron PN ^R P Pincer Complexes with Isonitrile Ligands Curley, Julia B.; Smith, Nicholas E.; Bernskoetter, Wesley H. Organometallics, Vol. 37, Issue 21 https://doi.org/10.1021/acs.organomet.8b00534	journal	October 2018
A Meeting of Metals—A Joint Virtual Issue between Organometallics and ACS Catalysis on First-Row Transition Metal Complexes Chirik, Paul J.; Gunnoe, T. Brent ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01831	journal	August 2015
Highly Efficient and Selective Hydrogenation of Aldehydes: A Well-Defined Fe(II) Catalyst Exhibits Noble-Metal Activity Gorgas, Nikolaus; Stöger, Berthold; Veiros, Luis F. ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.6b00436	journal	March 2016
Dehydrogenative Coupling of Ethanol and Ester Hydrogenation Catalyzed by Pincer-Type YNP Complexes Gusev, Dmitry G. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b02324	journal	September 2016
Selective Iron-Catalyzed N -Formylation of Amines using Dihydrogen and Carbon Dioxide Jayarathne, Upul; Hazari, Nilay; Bernskoetter, Wesley H. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03834	journal	January 2018
Opportunities and Challenges for Catalysis in Carbon Dioxide Utilization Burkart, Michael D.; Hazari, Nilay; Tway, Cathy L. ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b02113	journal	July 2019
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion Fürstner, Alois ACS Central Science, Vol. 2, Issue 11 https://doi.org/10.1021/acscentsci.6b00272	journal	October 2016
Iron(II) Complexes of the Linear rac- Tetraphos-1 Ligand as Efficient Homogeneous Catalysts for Sodium Bicarbonate Hydrogenation and Formic Acid Dehydrogenation Bertini, Federica; Mellone, Irene; Ienco, Andrea ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501998t	journal	January 2015
The Mechanism of Borane–Amine Dehydrocoupling with Bifunctional Ruthenium Catalysts Marziale, Alexander N.; Friedrich, Anja; Klopsch, Isabel Journal of the American Chemical Society, Vol. 135, Issue 36 https://doi.org/10.1021/ja311092c	journal	August 2013
Alcohol Amination with Ammonia Catalyzed by an Acridine-Based Ruthenium Pincer Complex: A Mechanistic Study Ye, Xuan; Plessow, Philipp N.; Brinks, Marion K. Journal of the American Chemical Society, Vol. 136, Issue 16 https://doi.org/10.1021/ja409368a	journal	April 2014
Lewis Acid-Assisted Formic Acid Dehydrogenation Using a Pincer-Supported Iron Catalyst Bielinski, Elizabeth A.; Lagaditis, Paraskevi O.; Zhang, Yuanyuan Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja505241x	journal	July 2014
Understanding the Individual and Combined Effects of Solvent and Lewis Acid on CO ₂ Insertion into a Metal Hydride Heimann, Jessica E.; Bernskoetter, Wesley H.; Hazari, Nilay Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b05192	journal	May 2019
Outer sphere hydrogenation catalysis Eisenstein, Odile; Crabtree, Robert H. New J. Chem., Vol. 37, Issue 1 https://doi.org/10.1039/C2NJ40659D	journal	January 2013
Selective conversion of alcohols in water to carboxylic acids by in situ generated ruthenium trans dihydrido carbonyl PNP complexes Choi, Jong-Hoo; Heim, Leo E.; Ahrens, Mike Dalton Trans., Vol. 43, Issue 46 https://doi.org/10.1039/C4DT01634C	journal	January 2014
Formic acid as a hydrogen storage material – development of homogeneous catalysts for selective hydrogen release Mellmann, Dörthe; Sponholz, Peter; Junge, Henrik Chemical Society Reviews, Vol. 45, Issue 14 https://doi.org/10.1039/C5CS00618J	journal	January 2016
Iron catalyzed CO ₂ hydrogenation to formate enhanced by Lewis acid co-catalysts Zhang, Yuanyuan; MacIntosh, Alex D.; Wong, Janice L. Chemical Science, Vol. 6, Issue 7 https://doi.org/10.1039/C5SC01467K	journal	January 2015
Nickel-catalyzed release of H ₂ from formic acid and a new method for the synthesis of zerovalent Ni(PMe ₃ ) ₄ Neary, Michelle C.; Parkin, Gerard Dalton Transactions, Vol. 45, Issue 37 https://doi.org/10.1039/C6DT01499B	journal	January 2016
Amide versus amine ligand paradigm in the direct amination of alcohols with Ru-PNP complexes Pingen, Dennis; Choi, Jong-Hoo; Allen, Henry Catalysis Science & Technology, Vol. 8, Issue 15 https://doi.org/10.1039/C8CY00869H	journal	January 2018
Acceleration of CO ₂ insertion into metal hydrides: ligand, Lewis acid, and solvent effects on reaction kinetics Heimann, Jessica E.; Bernskoetter, Wesley H.; Hazari, Nilay Chemical Science, Vol. 9, Issue 32 https://doi.org/10.1039/C8SC02535E	journal	January 2018
Hydrogen storage: beyond conventional methods Dalebrook, Andrew F.; Gan, Weijia; Grasemann, Martin Chemical Communications, Vol. 49, Issue 78 https://doi.org/10.1039/c3cc43836h	journal	January 2013
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006

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