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ACS Publications. Most Trusted. Most Cited. Most Read
Continuous-Flow Alkane Dehydrogenation by Supported Pincer-Ligated Iridium Catalysts at Elevated Temperatures

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Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Catal. 2018, 8, 9, 7828-7841
    Research Article

    Continuous-Flow Alkane Dehydrogenation by Supported Pincer-Ligated Iridium Catalysts at Elevated Temperatures
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    • Boris Sheludko
      Boris Sheludko
      Department of Chemistry and Chemical Biology  and  Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854, United States
      More by Boris Sheludko
    • Molly T. Cunningham
      Molly T. Cunningham
      Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854, United States
      More by Molly T. Cunningham
    • Alan S. Goldman
      Alan S. Goldman
      Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854, United States
      More by Alan S. Goldman
      Orcidhttp://orcid.org/0000-0002-2774-710X
    • Fuat E. Celik*
      Fuat E. Celik
      Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854, United States
      *F.E.C.: tel, +1 848 445 5558; e-mail, [email protected]
      More by Fuat E. Celik
      Orcidhttp://orcid.org/0000-0002-5891-6375
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    ACS Catalysis

    Cite this: ACS Catal. 2018, 8, 9, 7828–7841
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    https://doi.org/10.1021/acscatal.8b01497
    Published July 16, 2018
    Copyright © 2018 American Chemical Society
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    Abstract

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    Pincer-ligated iridium complexes of the form [Ir(R4PCP)L] (R4PCP = κ3-C6H3-2,6-(XPR2)2; X = CH2, O; R = tBu, iPr) are efficient homogeneous alkane dehydrogenation catalysts that have been reported to be highly active at temperatures of 240 °C or below. In this work, silica-supported [Ir(C2H4)(p-tBu2PO-tBu4POCOP)] (1/SiO2) was used to study a model continuous-flow gas-phase acceptorless alkane dehydrogenation system. This particular supported framework is thermally stable at temperatures up to 340 °C, 100 °C above the highest temperature at which analogous homogeneous complexes have been reported to show stable activity, with observed butane dehydrogenation rates of ca. 80 molbutenes molcat.–1 h–1. Solid-state 31P MAS NMR and ATR IR are used to demonstrate that the backbone pincer ligand remains intact and coordinated at 340 °C. The complex is fully converted to [Ir(CO)(p-tBu2PO-tBu4POCOP)] (3/SiO2) above 300 °C. 3/SiO2 is observed to be catalytically active at the higher temperatures tested, and reaction rates are comparable to those of 1/SiO2. 3/SiO2 and 1/SiO2 act as resting states for the active 14-electron fragment, through dissociation of the CO or olefin ligand, respectively. Given that 3/SiO2 is air resistant at ambient temperature and is structurally stable and catalytically active at elevated temperatures, it is a suitable candidate as a catalyst for the highly endothermic acceptorless dehydrogenation of alkanes.

    Copyright © 2018 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.8b01497.

    • 31P NMR of 3 in C6D6, 1H NMR of 3 in C6D6, 31P NMR of dihydride (4) and tetrahydride mixture in d8-toluene, 1H NMR of 4 in d8-toluene, color and appearance of catalyst, 31P MAS NMR of 4/SiO2, selectivity between butene isomers as a function of residence time and reaction temperature, and comparison of continuous-flow alkane dehydrogenation over 1/SiO2 and 2/SiO2 (PDF)

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    Cited By

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    This article is cited by 38 publications.

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    ACS Catalysis

    Cite this: ACS Catal. 2018, 8, 9, 7828–7841
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.8b01497
    Published July 16, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

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