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Reactions of 13-Vertex Carboranes with Strong Bases: Synthesis and Structural Characterization of Carborane Monoanions with exo-π Bonding

Authors

  • Fangrui Zheng,

    1. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong (China), Fax: (+852) 2603-5057
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  • Dr. Jian Zhang,

    1. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong (China), Fax: (+852) 2603-5057
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  • Xiaodu Fu,

    1. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong (China), Fax: (+852) 2603-5057
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  • Prof. Dr. Zuowei Xie

    Corresponding author
    1. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong (China), Fax: (+852) 2603-5057
    • Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong (China), Fax: (+852) 2603-5057

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Abstract

Several monoanions of 13-vertex carboranes were prepared in high yields from the reactions of C,C′-linked 13-vertex carboranes with tBuOK or NaH in dry THF at room temperature. These monoanions were characterized by various spectroscopic methods, elemental analysis, and single-crystal X-ray diffraction. The results showed substantial double-bond character between the cage-carbon atom and the exo vicinal carbon atom, thus leading to charge delocalization into the cage. As a result, the atom[BOND]atom distances within the cage were elongated, with one broken C[BOND]B bond. However, the cage geometry of the monoanions remained very similar to that of their corresponding neutral 13-vertex closo-carboranes. These monoanions represent the first examples of 13-vertex carboranes with exo-π bonding to hypercarbon atoms.

Abstract

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