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Activation of Alkynes by a Redox-Active Carboranyl Diphosphine and Formation of Boron-Containing Phosphacycles

  • Gayathri B. Gange
    Gayathri B. Gange
    Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter Street, Columbia, South Carolina 29208, United States
  • Amanda L. Humphries
    Amanda L. Humphries
    Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter Street, Columbia, South Carolina 29208, United States
  • Mark D. Smith
    Mark D. Smith
    Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter Street, Columbia, South Carolina 29208, United States
  • , and 
  • Dmitry V. Peryshkov*
    Dmitry V. Peryshkov
    Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter Street, Columbia, South Carolina 29208, United States
    *Email: [email protected]
Cite this: Inorg. Chem. 2022, 61, 46, 18568–18573
Publication Date (Web):November 9, 2022
https://doi.org/10.1021/acs.inorgchem.2c02919
Copyright © 2022 American Chemical Society

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    Abstract

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    In this work, we report the reactivity of the carboranyl diphosphine, 1-PtBu2–2-PiPr2-C2B10H10, with terminal alkynes, resulting in the formation of boron-containing phosphacycles. The reported system combines the nucleophilic activation of electron-deficient terminal alkynes via electron-rich phosphine groups with the redox behavior of carborane clusters to promote a sequence of metal-free intramolecular B–H bond activation and cyclization, creating an alkenylphosphonium cycle fused with a reduced open nido-carborane cluster.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c02919.

    • Characterization data (NMR spectra and crystallographic details), displacement ellipsoid plots, and computational method details (PDF)

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    CCDC 2084267 and 21934312193434 contain 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.

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