Manganese Mediated Formic Acid Dehydrogenation

Anderson, Nickolas H.; Boncella, James M.; Tondreau, Aaron Maurice

doi:10.1002/chem.201901177

Title: Manganese Mediated Formic Acid Dehydrogenation

Journal Article · Wed May 08 00:00:00 EDT 2019 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201901177· OSTI ID:1532714

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Abstract A robust and rapid manganese formic acid (FA) dehydrogenation catalyst is reported. The manganese is supported by the recently developed, hybrid backbone chelate ligand ^{t Bu} PNNOP ( ^{t Bu} PNNOP=2,6‐(di‐ tert ‐butylphosphinito)(di‐ tert ‐butylphosphinamine)pyridine) ( 1 ) and the catalyst is readily prepared with MnBrCO ₅ to form [( ^{t Bu} PNNOP)Mn(CO) ₂ ][Br] ( 2 ). Dehydrohalogenation of 2 generated the neutral five coordinate complex ( ^{t Bu} PNNOP)Mn(CO) ₂ ( 3 ). Dehydrogenation of FA by 2 and 3 was found to be highly efficient, exhibiting turnover frequencies (TOFs) exceeding 8500 h ⁻¹ , rivaling many noble metal systems. The parent chelate, ^{t Bu} PONOP ( ^{t Bu} PONOP=2,6‐bis(di‐ tert ‐butylphosphinito)pyridine) or ^{t Bu} PNNNP ( ^{t Bu} PNNNP=2,6‐bis (di‐ tert ‐butylphosphinamine)pyridine), coordination complexes of Mn were synthesized, respectively affording [( ^{t Bu} PONOP)Mn(CO) ₂ ][Br] ( 4 ) and [( ^{t Bu} PNNNP)Mn(CO) ₂ ][Br] ( 5 ). FA dehydrogenation with the hybrid‐ligand supported 2 exhibits superior catalysis to 4 and 5 .

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: 89233218CNA000001; Science Campaign 5

OSTI ID:: 1532714

Alternate ID(s):: OSTI ID: 1548850

Report Number(s):: LA-UR-18-31831

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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References (56)

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
Synthesis and Structure of Six-Coordinate Iron Borohydride Complexes Supported by PNP Ligands Koehne, Ingo; Schmeier, Timothy J.; Bielinski, Elizabeth A. Inorganic Chemistry, Vol. 53, Issue 4 https://doi.org/10.1021/ic402762v	journal	December 2013
Well-Defined Iron Catalysts for the Acceptorless Reversible Dehydrogenation-Hydrogenation of Alcohols and Ketones Chakraborty, Sumit; Lagaditis, Paraskevi O.; Förster, Moritz ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs5009656	journal	October 2014
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
Iron-Catalyzed Hydrogen Production from Formic Acid Boddien, Albert; Loges, Björn; Gärtner, Felix Journal of the American Chemical Society, Vol. 132, Issue 26 https://doi.org/10.1021/ja100925n	journal	July 2010
Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst Boddien, A.; Mellmann, D.; Gartner, F. Science, Vol. 333, Issue 6050 https://doi.org/10.1126/science.1206613	journal	September 2011
Efficient Hydrogen Liberation from Formic Acid Catalyzed by a Well-Defined Iron Pincer Complex under Mild Conditions Zell, Thomas; Butschke, Burkhard; Ben-David, Yehoshoa Chemistry - A European Journal, Vol. 19, Issue 25 https://doi.org/10.1002/chem.201301383	journal	May 2013
Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H ₂ : A Catalytic and Mechanistic Study Chakraborty, Subrata; Gellrich, Urs; Diskin-Posner, Yael Angewandte Chemie International Edition, Vol. 56, Issue 15 https://doi.org/10.1002/anie.201700681	journal	March 2017
Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H ₂ : A Catalytic and Mechanistic Study Chakraborty, Subrata; Gellrich, Urs; Diskin-Posner, Yael Angewandte Chemie, Vol. 129, Issue 15 https://doi.org/10.1002/ange.201700681	journal	March 2017
Newly designed manganese and cobalt complexes with pendant amines for the hydrogenation of CO ₂ to methanol: a DFT study Chen, Xiangyang; Ge, Hongyu; Yang, Xinzheng Catalysis Science & Technology, Vol. 7, Issue 2 https://doi.org/10.1039/C6CY01551D	journal	January 2017
Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese–PNN pincer complex Papa, Veronica; Cabrero-Antonino, Jose R.; Alberico, Elisabetta Chemical Science, Vol. 8, Issue 5 https://doi.org/10.1039/C7SC00138J	journal	January 2017
Non-Pincer-Type Manganese Complexes as Efficient Catalysts for the Hydrogenation of Esters van Putten, Robbert; Uslamin, Evgeny A.; Garbe, Marcel Angewandte Chemie International Edition, Vol. 56, Issue 26 https://doi.org/10.1002/anie.201701365	journal	April 2017
Non-Pincer-Type Manganese Complexes as Efficient Catalysts for the Hydrogenation of Esters van Putten, Robbert; Uslamin, Evgeny A.; Garbe, Marcel Angewandte Chemie, Vol. 129, Issue 26 https://doi.org/10.1002/ange.201701365	journal	April 2017
Manganese-catalyzed allylation via sequential C–H and C–C/C–Het bond activation Lu, Qingquan; Klauck, Felix J. R.; Glorius, Frank Chemical Science, Vol. 8, Issue 5 https://doi.org/10.1039/C7SC00230K	journal	January 2017
Highly Efficient and Robust Photocatalytic Systems for CO ₂ Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts Takeda, Hiroyuki; Kamiyama, Hiroko; Okamoto, Kouhei Journal of the American Chemical Society, Vol. 140, Issue 49 https://doi.org/10.1021/jacs.8b10619	journal	November 2018
Mechanism of the Manganese-Pincer-Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols Luque-Urrutia, Jesús A.; Solà, Miquel; Milstein, David Journal of the American Chemical Society, Vol. 141, Issue 6 https://doi.org/10.1021/jacs.8b11308	journal	January 2019
Mechanism of Coupling of Alcohols and Amines To Generate Aldimines and H ₂ by a Pincer Manganese Catalyst Masdemont, Judit; Luque-Urrutia, Jesús A.; Gimferrer, Martí ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04175	journal	January 2019
Homogeneous Catalysis by Cobalt and Manganese Pincer Complexes Mukherjee, Arup; Milstein, David ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b02869	journal	October 2018
Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study Tondreau, Aaron M.; Michalczyk, Ryszard; Boncella, James M. Organometallics, Vol. 36, Issue 21 https://doi.org/10.1021/acs.organomet.7b00618	journal	September 2017
1,2-Addition of Formic or Oxalic Acid to ^– N{CH ₂ CH ₂ (PiPr ₂ )} ₂ -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid Tondreau, Aaron M.; Boncella, James M. Organometallics, Vol. 35, Issue 12 https://doi.org/10.1021/acs.organomet.6b00274	journal	June 2016
A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol Andérez-Fernández, María; Vogt, Lydia K.; Fischer, Steffen Angewandte Chemie International Edition, Vol. 56, Issue 2 https://doi.org/10.1002/anie.201610182	journal	December 2016
A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol Andérez-Fernández, María; Vogt, Lydia K.; Fischer, Steffen Angewandte Chemie, Vol. 129, Issue 2 https://doi.org/10.1002/ange.201610182	journal	December 2016
A Viable Hydrogen-Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Catalyst Fellay, Céline; Dyson, Paul J.; Laurenczy, Gábor Angewandte Chemie International Edition, Vol. 47, Issue 21, p. 3966-3968 https://doi.org/10.1002/anie.200800320	journal	May 2008
A Viable Hydrogen-Storage System Based On Selective Formic Acid Decomposition with a Ruthenium Catalyst Fellay, Céline; Dyson, Paul J.; Laurenczy, Gábor Angewandte Chemie, Vol. 120, Issue 21 https://doi.org/10.1002/ange.200800320	journal	May 2008
Breakthroughs in Hydrogen Storage-Formic Acid as a Sustainable Storage Material for Hydrogen Joó, Ferenc ChemSusChem, Vol. 1, Issue 10 https://doi.org/10.1002/cssc.200800133	journal	October 2008
Carbon dioxide and formic acid—the couple for environmental-friendly hydrogen storage? Enthaler, Stephan; von Langermann, Jan; Schmidt, Thomas Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/b907569k	journal	January 2010
Catalytic Generation of Hydrogen from Formic acid and its Derivatives: Useful Hydrogen Storage Materials Loges, Björn; Boddien, Albert; Gärtner, Felix Topics in Catalysis, Vol. 53, Issue 13-14 https://doi.org/10.1007/s11244-010-9522-8	journal	May 2010
Formic Acid as a Hydrogen Energy Carrier Eppinger, Jörg; Huang, Kuo-Wei ACS Energy Letters, Vol. 2, Issue 1 https://doi.org/10.1021/acsenergylett.6b00574	journal	December 2016
Selective Formic Acid Decomposition for High-Pressure Hydrogen Generation: A Mechanistic Study Fellay, Céline; Yan, Ning; Dyson, Paul J. Chemistry - A European Journal, Vol. 15, Issue 15 https://doi.org/10.1002/chem.200801824	journal	February 2009
Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N ′-Diimine Ligand Guan, Chao; Zhang, Dan-Dan; Pan, Yupeng Inorganic Chemistry, Vol. 56, Issue 1 https://doi.org/10.1021/acs.inorgchem.6b02334	journal	December 2016
Simple Continuous High-Pressure Hydrogen Production and Separation System from Formic Acid under Mild Temperatures Iguchi, Masayuki; Himeda, Yuichiro; Manaka, Yuichi ChemCatChem, Vol. 8, Issue 5 https://doi.org/10.1002/cctc.201501296	journal	December 2015
Highly Robust Hydrogen Generation by Bioinspired Ir Complexes for Dehydrogenation of Formic Acid in Water: Experimental and Theoretical Mechanistic Investigations at Different pH Wang, Wan-Hui; Ertem, Mehmed Z.; Xu, Shaoan ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01090	journal	August 2015
Reversible hydrogen storage using CO₂ and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures Hull, Jonathan F.; Himeda, Yuichiro; Wang, Wan-Hui Nature Chemistry, Vol. 4, Issue 5, p. 383-388 https://doi.org/10.1038/nchem.1295	journal	March 2012
An efficient binuclear catalyst for decomposition of formic acid Gao, Yuan; Kuncheria, Joshi; Puddephatt, Richard J. Chemical Communications, Issue 21 https://doi.org/10.1039/a805789c	journal	January 1998
The interconversion of formic acid and hydrogen/carbon dioxide using a binuclear ruthenium complex catalyst Gao, Yuan; Kuncheria, Joshi K.; Jenkins, Hilary A. Journal of the Chemical Society, Dalton Transactions, Issue 18 https://doi.org/10.1039/b004234j	journal	January 2000
Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H ₂ /O ₂ Fuel Cells Loges, BjÃ¶rn; Boddien, Albert; Junge, Henrik Angewandte Chemie International Edition, Vol. 47, Issue 21 https://doi.org/10.1002/anie.200705972	journal	May 2008
Kontrollierte Wasserstofferzeugung aus Ameisensäure-Amin-Addukten bei Raumtemperatur und direkte Nutzung in H2/O2-Brennstoffzellen Loges, Björn; Boddien, Albert; Junge, Henrik Angewandte Chemie, Vol. 120, Issue 21 https://doi.org/10.1002/ange.200705972	journal	May 2008
Hydrogen Generation at Ambient Conditions: Application in Fuel Cells Boddien, Albert; Loges, Björn; Junge, Henrik ChemSusChem, Vol. 1, Issue 8-9 https://doi.org/10.1002/cssc.200800093	journal	September 2008
Continuous Hydrogen Generation from Formic Acid: Highly Active and Stable Ruthenium Catalysts Boddien, Albert; Loges, Björn; Junge, Henrik Advanced Synthesis & Catalysis, Vol. 351, Issue 14-15 https://doi.org/10.1002/adsc.200900431	journal	October 2009
The impact of Metal–Ligand Cooperation in Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium PNP Pincer Filonenko, Georgy A.; Conley, Matthew P.; Copéret, Christophe ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs4006869	journal	October 2013
Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP ₃ Mellone, Irene; Peruzzini, Maurizio; Rosi, Luca Dalton Trans., Vol. 42, Issue 7 https://doi.org/10.1039/C2DT32043F	journal	January 2013
Highly Efficient Reversible Hydrogenation of Carbon Dioxide to Formates Using a Ruthenium PNP-Pincer Catalyst Filonenko, Georgy A.; van Putten, Robbert; Schulpen, Erik N. ChemCatChem, Vol. 6, Issue 6 https://doi.org/10.1002/cctc.201402119	journal	April 2014
Formic Acid Dehydrogenation Catalysed by Tris(TPPTS) Ruthenium Species: Mechanism of the Initial “Fast” Cycle Thevenon, Arnaud; Frost-Pennington, Ewan; Weijia, Gan ChemCatChem, Vol. 6, Issue 11 https://doi.org/10.1002/cctc.201402410	journal	September 2014
Formic Acid As a Hydrogen Storage Medium: Ruthenium-Catalyzed Generation of Hydrogen from Formic Acid in Emulsions Czaun, Miklos; Goeppert, Alain; Kothandaraman, Jotheeswari ACS Catalysis, Vol. 4, Issue 1 https://doi.org/10.1021/cs4007974	journal	December 2013
Hydrogen Production by Selective Dehydrogenation of HCOOH Catalyzed by Ru-Biaryl Sulfonated Phosphines in Aqueous Solution Guerriero, Antonella; Bricout, Hervé; Sordakis, Katerina ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500655x	journal	August 2014
Efficient Disproportionation of Formic Acid to Methanol Using Molecular Ruthenium Catalysts Savourey, Solène; Lefèvre, Guillaume; Berthet, Jean-Claude Angewandte Chemie International Edition, Vol. 53, Issue 39 https://doi.org/10.1002/anie.201405457	journal	August 2014
Efficient Disproportionation of Formic Acid to Methanol Using Molecular Ruthenium Catalysts Savourey, Solène; Lefèvre, Guillaume; Berthet, Jean-Claude Angewandte Chemie, Vol. 126, Issue 39 https://doi.org/10.1002/ange.201405457	journal	August 2014
Ruthenium PNN(O) Complexes: Cooperative Reactivity and Application as Catalysts for Acceptorless Dehydrogenative Coupling Reactions de Boer, Sandra Y.; Korstanje, Ties J.; La Rooij, Stefan R. Organometallics, Vol. 36, Issue 8 https://doi.org/10.1021/acs.organomet.7b00111	journal	April 2017
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
A prolific catalyst for dehydrogenation of neat formic acid Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11308	journal	April 2016
Reactivity of Silanes with ( ^{t Bu} PONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition Anderson, Nickolas H.; Boncella, James M.; Tondreau, Aaron M. Chemistry - A European Journal, Vol. 23, Issue 55 https://doi.org/10.1002/chem.201703722	journal	September 2017
Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN ³ -Pincer Ligand Pan, Yupeng; Pan, Cheng-Ling; Zhang, Yufan Chemistry - An Asian Journal, Vol. 11, Issue 9 https://doi.org/10.1002/asia.201600169	journal	April 2016
Ligand Reactivity in Diarylamido/Bis(Phosphine) PNP Complexes of Mn(CO) ₃ and Re(CO) ₃ Radosevich, Alexander T.; Melnick, Jonathan G.; Stoian, Sebastian A. Inorganic Chemistry, Vol. 48, Issue 19 https://doi.org/10.1021/ic9010218	journal	October 2009
The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes Tondreau, Aaron M.; Boncella, James M. Polyhedron, Vol. 116 https://doi.org/10.1016/j.poly.2016.04.007	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
Reusable Homogeneous Catalytic System for Hydrogen Production from Methanol and Water Hu, Peng; Diskin-Posner, Yael; Ben-David, Yehoshoa ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500937f	journal	July 2014

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis
dehydrogenation
formic acid
manganese
PNNOP

CCDC 1894743: Experimental Crystal Structure Determination H., Anderson, Nickolas; James, Boncella,; M., Tondreau, Aaron https://doi.org/10.5517/ccdc.csd.cc21lmr1 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1894744: Experimental Crystal Structure Determination H., Anderson, Nickolas; James, Boncella,; M., Tondreau, Aaron https://doi.org/10.5517/ccdc.csd.cc21lms2 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1894745: Experimental Crystal Structure Determination H., Anderson, Nickolas; James, Boncella,; M., Tondreau, Aaron https://doi.org/10.5517/ccdc.csd.cc21lmt3 The current record is supplemented by this dataset	dataset	January 2019

Title: Manganese Mediated Formic Acid Dehydrogenation

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