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Catalytic Dehydrogenative C–C Coupling by a Pincer-Ligated Iridium Complex

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    Catalytic Dehydrogenative C–C Coupling by a Pincer-Ligated Iridium Complex
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    † Department of Chemistry, University of Rochester, Rochester, New York 14627, United States
    ‡ Department of Chemistry, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States
    *[email protected]
    *[email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2017, 139, 26, 8977–8989
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    https://doi.org/10.1021/jacs.7b03433
    Published June 8, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    The pincer-iridium fragment (iPrPCP)Ir (RPCP = κ3-2,6-C6H3(CH2PR2)2) has been found to catalyze the dehydrogenative coupling of vinyl arenes to afford predominantly (E,E)-1,4-diaryl-1,3-butadienes. The eliminated hydrogen can undergo addition to another molecule of vinyl arene, resulting in an overall disproportionation reaction with 1 equiv of ethyl arene formed for each equivalent of diarylbutadiene produced. Alternatively, sacrificial hydrogen acceptors (e.g., tert-butylethylene) can be added to the solution for this purpose. Diarylbutadienes are isolated in moderate to good yields, up to ca. 90% based on the disproportionation reaction. The results of DFT calculations and experiments with substituted styrenes indicate that the coupling proceeds via double C–H addition of a styrene molecule, at β-vinyl and ortho-aryl positions, to give an iridium(III) metalloindene intermediate; this intermediate then adds a β-vinyl C–H bond of a second styrene molecule before reductively eliminating product. Several metalloindene complexes have been isolated and crystallographically characterized. In accord with the proposed mechanism, substitution at the ortho-aryl positions of the styrene precludes dehydrogenative homocoupling. In the case of 2,4,6-trimethylstyrene, dehydrogenative coupling of β-vinyl and ortho-methyl C–H bonds affords dimethylindene, demonstrating that the dehydrogenative coupling is not limited to C(sp2)–H bonds.

    Copyright © 2017 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/jacs.7b03433. Crystallographic data are also deposited as CCDC nos. 1540144, 1540145, 1540146, 1539909, 1539910, 1539911, 1539912, and 1539913.

    • Full experimental details, characterization data, and NMR spectra (PDF)

    • X-ray crystallographic information including data collection parameters, bond lengths, fractional atomic coordinates, and anisotropic thermal parameters for 2–5, 7–9, and (E,E)-1,4-(2-naphthyl)-1,3-butadiene (PDF)

    • Reaction mechanisms and free energies, including Figures S1–S6 and Tables S1–S7, and optimized geometries and absolute energies (PDF)

    • Collection of .mol2 formatted files (ZIP)

    • Crystallographic data for 2 (CIF)

    • Crystallographic data for 3 (CIF)

    • Crystallographic data for 4 (CIF)

    • Crystallographic data for 5 (CIF)

    • Crystallographic data for 7 (CIF)

    • Crystallographic data for 8 (CIF)

    • Crystallographic data for 9 (CIF)

    • Crystallographic data for (E,E)-1,4-(2-naphthyl)-1,3-butadiene (CIF)

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    Cite this: J. Am. Chem. Soc. 2017, 139, 26, 8977–8989
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.7b03433
    Published June 8, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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