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Hybrid Inorganic–Organic Cross-Metathesis between Diborenes and Acetylene

  • Marcel Härterich
    Marcel Härterich
    Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
  • Benedikt Ritschel
    Benedikt Ritschel
    Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
  • Merle Arrowsmith
    Merle Arrowsmith
    Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
  • Julian Böhnke
    Julian Böhnke
    Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
  • Ivo Krummenacher
    Ivo Krummenacher
    Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
  • Ashwini K. Phukan*
    Ashwini K. Phukan
    Department of Chemical Sciences, Tezpur University, Tezpur 784028, Assam, India
    *Email [email protected]
  • , and 
  • Holger Braunschweig*
    Holger Braunschweig
    Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany
    *Email [email protected]
Cite this: J. Am. Chem. Soc. 2021, 143, 43, 18339–18345
Publication Date (Web):October 22, 2021
https://doi.org/10.1021/jacs.1c10131
Copyright © 2021 American Chemical Society

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    Abstract

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    The ruthenium-catalyzed cross-metathesis of alkenes and alkynes, which splits the alkene C═C double bond and couples one-half to each carbon of the alkyne C≡C triple bond, is one of the most efficient tools for the synthesis of 1,3-dienes, with wide-ranging applications, including pharmaceutical and polymer chemistry. In contrast, inorganic main-group metathesis reactions are restricted to a handful of examples of heavier p-block multiple bonds (P═P, Ge═Ge, and E≡E, E = Ge, Sn, Pb). We now report the first examples of thermally induced, transition-metal-free cross-metathesis between an organic alkyne and inorganic cyclic alkyl(amino)carbene (CAAC)-stabilized B═B double bonds, which yield fully planar, π-delocalized 1,8-diaza-3,6-diboraoctatetraenes. Density functional theory studies show that these compounds have an open-shell singlet biradical ground state with a thermally accessible closed-shell state. In-depth computational mechanistic analyses show that they are formed via a biradical cycloaddition–cycloreversion mechanism. Finally, unlike their organic counterparts, these B,N-analogues of octatetraene can undergo two-electron chemical reduction to form diamagnetic dianions.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c10131.

    • Experimental Section, plots of NMR, UV–vis, IR, and EPR spectra for new compounds, and complete details of crystallographic experiments and computational calculations (PDF)

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    CCDC 21071052107110 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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    Cited By

    This article is cited by 7 publications.

    1. Shiwei Lü, Zipeng Wang, Xiang Gao, Kai Chen, Shifa Zhu. 1,2‐Difunctionalization of Acetylene Enabled by Light. Angewandte Chemie 2023, 13 https://doi.org/10.1002/ange.202300268
    2. Shiwei Lü, Zipeng Wang, Xiang Gao, Kai Chen, Shifa Zhu. 1,2‐Difunctionalization of Acetylene Enabled by Light. Angewandte Chemie International Edition 2023, 58 https://doi.org/10.1002/anie.202300268
    3. Shicheng Dong, Jun Zhu. Predicting Small Molecule Activation including Catalytic Hydrogenation of Dinitrogen Promoted by a Dual Lewis Acid. Chemistry – An Asian Journal 2023, 18 (1) https://doi.org/10.1002/asia.202200991
    4. Bo Yang, Shaodong Lu, Yongdong Wang, Shifa Zhu. Diverse synthesis of C2-linked functionalized molecules via molecular glue strategy with acetylene. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-29556-2
    5. Jun Fan, Pei‐Ting Chia, Zheng‐Feng Zhang, Ming‐Chung Yang, Ming‐Der Su, Cheuk‐Wai So. A Pyridine‐Stabilized N ‐Phosphinoamidinato N ‐Heterocyclic Carbene‐Diboravinyl Cation: Boron Analogue of Vinyl Cation. Angewandte Chemie 2022, 134 (46) https://doi.org/10.1002/ange.202212842
    6. Jun Fan, Pei‐Ting Chia, Zheng‐Feng Zhang, Ming‐Chung Yang, Ming‐Der Su, Cheuk‐Wai So. A Pyridine‐Stabilized N ‐Phosphinoamidinato N ‐Heterocyclic Carbene‐Diboravinyl Cation: Boron Analogue of Vinyl Cation. Angewandte Chemie International Edition 2022, 61 (46) https://doi.org/10.1002/anie.202212842
    7. Felipe Fantuzzi, Yinchun Jiao, Rian D. Dewhurst, Frank Weinhold, Holger Braunschweig, Bernd Engels. Can a Wanzlick-like equilibrium exist between dicoordinate borylenes and diborenes?. Chemical Science 2022, 13 (18) , 5118-5129. https://doi.org/10.1039/D1SC05988B

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