ACS Publications. Most Trusted. Most Cited. Most Read
Amine Boranes Dehydrogenation Mediated by an Unsymmetrical Iridium Pincer Hydride: (PCN) vs (PCP) Improved Catalytic Performance

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Organometallics 2018, 37, 18, 3142-3153
    Article

    Amine Boranes Dehydrogenation Mediated by an Unsymmetrical Iridium Pincer Hydride: (PCN) vs (PCP) Improved Catalytic Performance
    Click to copy article linkArticle link copied!

    • Lapo Luconi
      Lapo Luconi
      Istituto di Chimica dei Composti Organometallici − Consiglio Nazionale delle Ricerche (ICCOM - CNR), Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy
      More by Lapo Luconi
    • Elena S. Osipova
      Elena S. Osipova
      A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilova Str. 28, 119991 Moscow, Russia
      More by Elena S. Osipova
    • Giuliano Giambastiani*
      Giuliano Giambastiani
      Istituto di Chimica dei Composti Organometallici − Consiglio Nazionale delle Ricerche (ICCOM - CNR), Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy
      Institute of Chemistry and Processes for Energy, Environment and Health (ICPEES), UMR 7515 CNRS - University of Strasbourg (UdS), 25, rue Becquerel, 67087 Strasbourg Cedex 02, France
      Kazan Federal University, Kremlyovskaya Str. 18, 420008 Kazan, Russia
      *E-mail: [email protected] (G.G.).
      More by Giuliano Giambastiani
      Orcidhttp://orcid.org/0000-0002-0315-3286
    • Maurizio Peruzzini
      Maurizio Peruzzini
      Istituto di Chimica dei Composti Organometallici − Consiglio Nazionale delle Ricerche (ICCOM - CNR), Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy
      More by Maurizio Peruzzini
    • Andrea Rossin*
      Andrea Rossin
      Istituto di Chimica dei Composti Organometallici − Consiglio Nazionale delle Ricerche (ICCOM - CNR), Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy
      *E-mail: [email protected] (A.R.).
      More by Andrea Rossin
      Orcidhttp://orcid.org/0000-0002-1283-2803
    • Natalia V. Belkova*
      Natalia V. Belkova
      A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilova Str. 28, 119991 Moscow, Russia
      *E-mail: [email protected] (N.V.B.).
      More by Natalia V. Belkova
      Orcidhttp://orcid.org/0000-0001-9346-8208
    • Oleg A. Filippov
      Oleg A. Filippov
      A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilova Str. 28, 119991 Moscow, Russia
      More by Oleg A. Filippov
      Orcidhttp://orcid.org/0000-0002-7963-2806
    • Ekaterina M. Titova
      Ekaterina M. Titova
      A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilova Str. 28, 119991 Moscow, Russia
      Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklay St, 117198 Moscow, Russia
      More by Ekaterina M. Titova
    • Alexander A. Pavlov
      Alexander A. Pavlov
      A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilova Str. 28, 119991 Moscow, Russia
      More by Alexander A. Pavlov
    • Elena S. Shubina*
      Elena S. Shubina
      A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS), Vavilova Str. 28, 119991 Moscow, Russia
      *E-mail: [email protected] (E.S.S.).
      More by Elena S. Shubina
      Orcidhttp://orcid.org/0000-0001-8057-3703
    Other Access OptionsSupporting Information (2)

    Organometallics

    Cite this: Organometallics 2018, 37, 18, 3142–3153
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.8b00488
    Published August 29, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The IrIII hydride (tBuPCN)IrHCl (1) containing the tridendate unsymmetrical pincer ligand tBuPCN– {tBuPCN(H) = 1-[3-[(di-tert-butylphosphino)methyl]phenyl]-1H-pyrazole} has been exploited as ammonia borane (NH3BH3, AB) and amine boranes dehydrogenation catalyst in THF solution at ambient temperature. 1 releases one H2 equivalent per AB equivalent, with concomitant cyclic poly(aminoboranes) formation [B-(cyclotriborazanyl)-amine-borane (BCTB) and cyclotriborazane (CTB)] as the final “spent fuel”. 1 has been found to have superior catalytic activity than its symmetrical analogue (tBuPCP)IrHCl, with recorded TOF values of 580 h–1 (AB in THF) and 401 h–1 (DMAB in toluene) at ambient temperature. The reaction has been analyzed experimentally through multinuclear [11B, 31P{1H}, 1H] NMR and IR spectroscopy, kinetic rate measurements, and kinetic isotope effect determination with deuterated AB isotopologues. The hydride/borohydride intermediate (tBuPCN)IrH(η2-BH4) (2) is the catalyst resting state formed during the dehydrogenation process; it is detected by a variable-temperature multinuclear NMR of the reaction course (in the 190–323 K range). A DFT modeling of the reaction mechanism using DMAB as substrate has been performed with the geometry optimization in toluene at the M06 level of theory. The combination of the kinetic and computational data reveals that a simultaneous B–H/N–H activation occurs in the presence of 1, after the preliminary amine borane coordination to the metal center.

    Copyright © 2018 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.8b00488.

    • Table S1: crystal data and structure refinement for 1. Figures S1–S25: 1H, 13C{1H}, 31P{1H}, 11B{1H} NMR spectra, UV–vis spectra, Man on the Moon device, AB dehydrogenation kinetics, FTIR spectrum, IR spectra, optimized geometries, energy profile (PDF)

    • Cartesian coordinates (XYZ)

    Accession Codes

    CCDC 1838328 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 38 publications.

    1. Amrita Gogoi, Mudit Dixit, Sourav Pal. Mechanistic Insight of High-Valent First-Row Transition Metal Complexes for Dehydrogenation of Ammonia Borane. The Journal of Physical Chemistry A 2024, 128 (37) , 7804-7815. https://doi.org/10.1021/acs.jpca.4c04069
    2. Wenjun Jiang, Chao Fu, Gaoyi Li, Shuang Zhang, Donghui Xu, Laicai Li. Theoretical Investigation on the Catalytic Performance of g-C3N4 Supported Single Metal Atom Catalysts for Hydrogen Evolution from NH3BH3. Organometallics 2024, 43 (1) , 48-54. https://doi.org/10.1021/acs.organomet.3c00347
    3. Itxaso Bustos, Jose M. Seco, Antonio Rodriguez-Dieguez, María A. Garralda, Claudio Mendicute-Fierro. Formation of Irida-β-ketoimines and PCNamine-Ir(III) Complexes by Reacting Irida-β-diketones with Aliphatic Diamines: Catalytic Activity in Hydrogen Release by Methanolysis of H3N–BH3. Organometallics 2022, 41 (23) , 3654-3663. https://doi.org/10.1021/acs.organomet.2c00451
    4. Claire N. Brodie, Lia Sotorrios, Timothy M. Boyd, Stuart A. Macgregor, Andrew S. Weller. Dehydropolymerization of H3B·NMeH2 Mediated by Cationic Iridium(III) Precatalysts Bearing κ3-iPr-PNRP Pincer Ligands (R = H, Me): An Unexpected Inner-Sphere Mechanism. ACS Catalysis 2022, 12 (20) , 13050-13064. https://doi.org/10.1021/acscatal.2c03778
    5. Claire N. Brodie, Timothy M. Boyd, Lia Sotorríos, David E. Ryan, Eimear Magee, Steven Huband, James S. Town, Guy C. Lloyd-Jones, David M. Haddleton, Stuart A. Macgregor, Andrew S. Weller. Controlled Synthesis of Well-Defined Polyaminoboranes on Scale Using a Robust and Efficient Catalyst. Journal of the American Chemical Society 2021, 143 (49) , 21010-21023. https://doi.org/10.1021/jacs.1c10888
    6. Lara Cancela, Miguel A. Esteruelas, Montserrat Oliván, Enrique Oñate. Azolium Control of the Osmium-Promoted Aromatic C–H Bond Activation in 1,3-Disubstituted Substrates. Organometallics 2021, 40 (23) , 3979-3991. https://doi.org/10.1021/acs.organomet.1c00565
    7. Isabel Ortega-Lepe, Andrea Rossin, Práxedes Sánchez, Laura L. Santos, Nuria Rendón, Eleuterio Álvarez, Joaquín López-Serrano, Andrés Suárez. Ammonia–Borane Dehydrogenation Catalyzed by Dual-Mode Proton-Responsive Ir-CNNH Complexes. Inorganic Chemistry 2021, 60 (23) , 18490-18502. https://doi.org/10.1021/acs.inorgchem.1c03056
    8. Abhishek Kumar, Jusaina Eyyathiyil, Joyanta Choudhury. Reduction of Carbon Dioxide with Ammonia-Borane under Ambient Conditions: Maneuvering a Catalytic Way. Inorganic Chemistry 2021, 60 (15) , 11684-11692. https://doi.org/10.1021/acs.inorgchem.1c01803
    9. Kaj M. van Vliet, Lara H. Polak, Maxime A. Siegler, Jarl Ivar van der Vlugt, Célia Fonseca Guerra, Bas de Bruin. Efficient Copper-Catalyzed Multicomponent Synthesis of N-Acyl Amidines via Acyl Nitrenes. Journal of the American Chemical Society 2019, 141 (38) , 15240-15249. https://doi.org/10.1021/jacs.9b07140
    10. Sanghamitra Das, Vasudevan Subramaniyan, Ganesan Mani. Nickel(II) and Palladium(II) Complexes Bearing an Unsymmetrical Pyrrole-Based PNN Pincer and Their Norbornene Polymerization Behaviors versus the Symmetrical NNN and PNP Pincers. Inorganic Chemistry 2019, 58 (5) , 3444-3456. https://doi.org/10.1021/acs.inorgchem.8b03562
    11. Amrita Gogoi, Mudit Dixit, Sourav Pal. Modelling an Fe‐III High‐Valent Pincer‐type Transition Metal Complex for Dehydrogenation of Ammonia‐Borane. Chemistry – An Asian Journal 2025, 424 https://doi.org/10.1002/asia.202401976
    12. Panayiota Adamou, Silvio Bellomi, Eleana Harkou, Xiaowei Chen, Juan J. Delgado, Nikolaos Dimitratos, George Manos, Alberto Villa, Achilleas Constantinou. Hydrous hydrazine decomposition over Rh/Al2O3 catalyst: Experimental and CFD studies. Chemical Engineering Journal 2024, 493 , 152715. https://doi.org/10.1016/j.cej.2024.152715
    13. R. I. Nekrasov, T. A. Peganova, A. M. Kal´sin, N. V. Belkova. Half-Sandwich Iminophosphonamide Rhodium Complexes as Highly Efficient Catalysts for Dehydrogenation of Dimethylamine-Borane. Koordinacionnaâ himiâ 2024, 50 (6) , 394-401. https://doi.org/10.31857/S0132344X24060053
    14. E. S. Gulyaeva, E. I. Gutsul, Y. V. Nelyubina, E. S. Osipova, O. A. Filippov, E. S. Shubina, N. V. Belkova. Isonitrile Coordination to Pincer Iridium Hydrido Chlorides. Russian Journal of Coordination Chemistry 2024, 50 (5) , 316-325. https://doi.org/10.1134/S1070328423601541
    15. R. I. Nekrasov, T. A. Peganova, A. M. Kal’sin, N. V. Belkova. Half-Sandwich Iminophosphonamide Rhodium Complexes as Highly Efficient Catalysts for Dehydrogenation of Dimethylamine-Borane. Russian Journal of Coordination Chemistry 2024, 50 (5) , 343-348. https://doi.org/10.1134/S1070328424600098
    16. Louis Le Moigne, Tommaso Posenato, David Gajan, Jennifer Lesage de la Haye, Jean Raynaud, Emmanuel Lacôte. Catalyst‐Free Transfer Hydrogenation from Amine‐Borane Small Oligomers. Chemistry – A European Journal 2024, 30 (1) https://doi.org/10.1002/chem.202300145
    17. Vasudha Sharma, Amaleswari Rasamsetty, Chinmoy Das, Dipanti Borah, Maheswaran Shanmugam. A robust low coordinate Co(II) catalyst for efficient conversion of CO2 into methanol under mild conditions. Chemical Engineering Journal 2023, 474 , 145714. https://doi.org/10.1016/j.cej.2023.145714
    18. Marta Delgado Gómez, Marco Marazzi, José Elguero, Maxime Ferrer, Ibon Alkorta. Production of Dihydrogen Using Ammonia Borane as Reagent and Pyrazole as Catalyst. ChemPhysChem 2023, 24 (17) https://doi.org/10.1002/cphc.202300214
    19. Silvio Bellomi, Ilaria Barlocco, Xiaowei Chen, Juan J. Delgado, Rosa Arrigo, Nikolaos Dimitratos, Alberto Roldan, Alberto Villa. Enhanced stability of sub-nanometric iridium decorated graphitic carbon nitride for H 2 production upon hydrous hydrazine decomposition. Physical Chemistry Chemical Physics 2023, 25 (2) , 1081-1095. https://doi.org/10.1039/D2CP04387D
    20. Elena S. Osipova, Ekaterina S. Gulyaeva, Nikolay V. Kireev, Sergey A. Kovalenko, Christian Bijani, Yves Canac, Dmitry A. Valyaev, Oleg A. Filippov, Natalia V. Belkova, Elena S. Shubina. Fac -to- mer isomerization triggers hydride transfer from Mn( i ) complex fac -[(dppm)Mn(CO) 3 H]. Chemical Communications 2022, 58 (32) , 5017-5020. https://doi.org/10.1039/D2CC00999D
    21. Vladislava A. Kirkina, Alexander A. Kissel, Alexander N. Selikhov, Yulia V. Nelyubina, Oleg A. Filippov, Natalia V. Belkova, Alexander A. Trifonov, Elena S. Shubina. Amine-boranes reactions promoted by lanthanide( ii ) ions. Chemical Communications 2022, 58 (6) , 859-862. https://doi.org/10.1039/D1CC06401K
    22. Hugo Valdés, Rebeca Osorio-Yañez, Ernesto Rufino-Felipe, David Morales-Morales. Organometallic Pincer Complexes of Cobalt, Rhodium, and Iridium. 2022, 816-867. https://doi.org/10.1016/B978-0-12-820206-7.00145-1
    23. Zufar N. Gafurov, Ekaterina M. Zueva, Giyjaz E. Bekmukhamedov, Alexey A. Kagilev, Artyom O. Kantyukov, Ilya K. Mikhailov, Khasan R. Khayarov, Maria M. Petrova, Alexey P. Dovzhenko, Andrea Rossin, Giuliano Giambastiani, Dmitry G. Yakhvarov. Benzothiazole- vs. pyrazole-based unsymmetrical (PCN) pincer complexes of nickel(II) as homogeneous catalysts in ethylene oligomerization. Journal of Organometallic Chemistry 2021, 949 , 121951. https://doi.org/10.1016/j.jorganchem.2021.121951
    24. Natalia V. Belkova, Oleg A. Filippov, Elena S. Osipova, Sergey V. Safronov, Lina M. Epstein, Elena S. Shubina. Influence of phosphine (pincer) ligands on the transition metal hydrides reactivity. Coordination Chemistry Reviews 2021, 438 , 213799. https://doi.org/10.1016/j.ccr.2021.213799
    25. Zufar N. Gafurov, Artyom O. Kantyukov, Alexey A. Kagilev, Alina A. Kagileva, Il’yas F. Sakhapov, Ilya K. Mikhailov, Dmitry G. Yakhvarov. Recent Advances in Chemistry of Unsymmetrical Phosphorus-Based Pincer Nickel Complexes: From Design to Catalytic Applications. Molecules 2021, 26 (13) , 4063. https://doi.org/10.3390/molecules26134063
    26. Shrinwantu Pal, Takanori Iwasaki, Kyoko Nozaki. Metal–ligand cooperative κ 1 - N -pyrazolate Cp*Rh III -catalysts for dehydrogenation of dimethylamine-borane at room temperature. Dalton Transactions 2021, 50 (23) , 7938-7943. https://doi.org/10.1039/D1DT01705E
    27. Patrick Hasche, Julia Haak, Felix Anke, Christoph Kubis, Wolfgang Baumann, Hans-Joachim Drexler, Haijun Jiao, Torsten Beweries. Dehydropolymerisation of methylamine borane using highly active rhodium( iii ) bis(thiophosphinite) pincer complexes: catalytic and mechanistic insights. Catalysis Science & Technology 2021, 11 (10) , 3514-3526. https://doi.org/10.1039/D1CY00124H
    28. Umit B. Demirci. Mechanistic insights into the thermal decomposition of ammonia borane, a material studied for chemical hydrogen storage. Inorganic Chemistry Frontiers 2021, 8 (7) , 1900-1930. https://doi.org/10.1039/D0QI01366H
    29. Lapo Luconi, Giulia Tuci, Zufar N. Gafurov, Giorgio Mercuri, Alexey A. Kagilev, Claudio Pettinari, Vladimir I. Morozov, Dmitry G. Yakhvarov, Andrea Rossin, Giuliano Giambastiani. Unsymmetrical nickel (PCN) pincer complexes with a benzothiazole side-arm: Synthesis, characterization and electrochemical properties. Inorganica Chimica Acta 2021, 517 , 120182. https://doi.org/10.1016/j.ica.2020.120182
    30. Vladislava A. Kirkina, Elena S. Osipova, Oleg A. Filippov, Gleb A. Silantyev, Dmitri Gelman, Elena S. Shubina, Natalia V. Belkova. Dehydrogenation of amine–boranes catalyzed by a PC s p 3 P pincer iridium complex. Mendeleev Communications 2020, 30 (3) , 276-278. https://doi.org/10.1016/j.mencom.2020.05.004
    31. Sanghamitra Das, Vasudevan Subramaniyan, Munmun Mondal, Ganesan Mani. Synthesis, X‐Ray Structures, and Fluxional Properties of Symmetrical, Asymmetrical Binuclear and Cubane Type Copper(I) Complexes Bearing the Pyrrole‐Based P, N‐Hetero Donor Ligand. ChemistrySelect 2020, 5 (16) , 5006-5012. https://doi.org/10.1002/slct.202001312
    32. Zufar N. Gafurov, Giyjaz E. Bekmukhamedov, Alexey A. Kagilev, Artyom O. Kantyukov, Il’yas F. Sakhapov, Ilya K. Mikhailov, Khasan R. Khayarov, Ruslan B. Zaripov, Daut R. Islamov, Konstantin S. Usachev, Lapo Luconi, Andrea Rossin, Giuliano Giambastiani, Dmitry G. Yakhvarov. Unsymmetrical pyrazole-based PCN pincer NiII halides: Reactivity and catalytic activity in ethylene oligomerization. Journal of Organometallic Chemistry 2020, 912 , 121163. https://doi.org/10.1016/j.jorganchem.2020.121163
    33. Takuya Shimbayashi, Ken-ichi Fujita. Metal-catalyzed hydrogenation and dehydrogenation reactions for efficient hydrogen storage. Tetrahedron 2020, 76 (11) , 130946. https://doi.org/10.1016/j.tet.2020.130946
    34. Itxaso Bustos, Jose M. Seco, Antonio Rodríguez-Diéguez, María A. Garralda, Claudio Mendicute-Fierro. Acyl(furfurylamine)iridium(III) complexes from irida-β-diketones. Characterisation and catalytic activity in amine-borane hydrolysis. Inorganica Chimica Acta 2019, 498 , 119165. https://doi.org/10.1016/j.ica.2019.119165
    35. Lapo Luconi, Umit B. Demirci, Maurizio Peruzzini, Giuliano Giambastiani, Andrea Rossin. Ammonia borane and hydrazine bis(borane) dehydrogenation mediated by an unsymmetrical (PNN) ruthenium pincer hydride: metal–ligand cooperation for hydrogen production. Sustainable Energy & Fuels 2019, 3 (10) , 2583-2596. https://doi.org/10.1039/C9SE00241C
    36. Elena S. Osipova, Ekaterina S. Gulyaeva, Oleg A. Filippov, Sergey V. Safronov, Alexander A. Pavlov, Alexey V. Polukeev, Vladislava A. Kirkina, Ekaterina M. Titova, Elena S. Shubina, Natalia V. Belkova. Effect of Ligands on the Lewis Acidity of the Metal and the Binding of N‐Bases to Iridium Pincer Complexes. European Journal of Inorganic Chemistry 2019, 2019 (10) , 1389-1397. https://doi.org/10.1002/ejic.201801341
    37. Elena S. Osipova, Oleg A. Filippov, Elena S. Shubina, Natalia V. Belkova. Non-covalent interactions in stoichiometric and catalytic reactions of iridium pincer complexes. Mendeleev Communications 2019, 29 (2) , 121-127. https://doi.org/10.1016/j.mencom.2019.03.001
    38. Thomas M. Maier, Sebastian Sandl, Ilya G. Shenderovich, Axel Jacobi von Wangelin, Jan J. Weigand, Robert Wolf. Amine‐Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α‐Diimine Cobaltates. Chemistry – A European Journal 2019, 25 (1) , 238-245. https://doi.org/10.1002/chem.201804811
    Download PDF
    Go to Organometallics
    Get e-Alerts
    Get e-Alerts

    Organometallics

    Cite this: Organometallics 2018, 37, 18, 3142–3153
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.8b00488
    Published August 29, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Article Views

    1212

    Altmetric

    -

    Citations

    38
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.