En Route to Dinitroacetylene: Nitro(trimethylsilyl)acetylene and Nitroacetylene Harnessed by Dicobalt Hexacarbonyl

Authors

  • Dr. G. Kenneth Windler,

    1. Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
    2. High Explosives Application Facility, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (USA)
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  • Dr. Mao-Xi Zhang,

    1. High Explosives Application Facility, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (USA)
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  • Robert Zitterbart,

    1. Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
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  • Dr. Philip F. Pagoria,

    1. High Explosives Application Facility, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550 (USA)
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  • Prof. K. Peter C. Vollhardt

    Corresponding author
    1. Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
    • Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
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Abstract

Dinitroacetylene and other nitroacetylenes are attractive stoichiometric precursors to high energy-density materials, but suffer from high reactivity and thermal instability. Herein, we report that nitroacetylenes can be dramatically stabilized in the form of their dicobalt hexacarbonyl complexes. In particular, we describe the syntheses and characterization of the first two transition-metal complexes of nitroalkynes, [μ-1-nitro-2-(trimethylsilyl)ethyne-1,2-diyl]bis(tricarbonylcobalt)(CoCo) and [μ-1-nitroethyne-1,2-diyl]bis(tricarbonylcobalt)(CoCo). The chemistry of these compounds reveals their potential as reaction partners in [2+2+2] cyclotrimerizations, furnishing nitroindane, nitrotetralin, and trinitrobenzene products. The X-ray crystal structure of 1,3,5-trinitro-2,4,6-tris(trimethylsilyl)benzene presents a distorted, yet planar, aromatic ring.

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