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Bismuthanylstibanes.

Katherine M Marczenko1, Saurabh S Chitnis

  • 1Department of Chemistry, Dalhousie University, 6274 Coburg Road, Halifax, Nova Scotia B3H 4R2, Canada. Saurabh.chitnis@dal.ca.

Chemical Communications (Cambridge, England)
|February 7, 2020
PubMed
Summary

Researchers synthesized thermally-robust bismuthanylstibanes, showcasing the first neutral bismuth-antimony (Bi-Sb) sigma bonds in a solid state. This breakthrough enables new avenues in inorganic chemistry and materials science.

Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Neutral sigma bonds between bismuth and antimony (Bi-Sb) are highly reactive and challenging to isolate.
  • Stabilizing such bonds requires specific molecular scaffolds that can support otherwise labile linkages.

Purpose of the Study:

  • To develop a facile and high-yield synthetic route for compounds featuring neutral Bi-Sb sigma bonds.
  • To investigate the structural and electronic properties of these novel bismuthanylstibanes.
  • To explore the reactivity of the newly formed Bi-Sb bond.

Main Methods:

  • A one-step reaction was employed for the synthesis of bismuthanylstibanes.
  • Density Functional Theory (DFT) calculations were utilized to understand the stabilizing effect of the scaffold.

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  • Reactions with ammonia borane and elemental sulfur were performed to probe the Bi-Sb bond's chemistry.

    • Main Results:

    • Thermally-robust bismuthanylstibanes were successfully prepared in high yield.
    • The study presents the first examples of neutral Bi-Sb sigma bonds isolated in the solid state.
    • DFT calculations confirmed the stabilizing role of the bis(silylamino)naphthalene ligand.
    • The reactivity of the Bi-Sb bond was demonstrated through fission with ammonia borane and insertion of a sulfur atom.
    • The first Bi-S-Sb motif was synthesized.

    Conclusions:

    • A robust synthetic method for creating stable neutral Bi-Sb sigma bonds has been established.
    • The bis(silylamino)naphthalene scaffold effectively stabilizes these otherwise labile bonds.
    • The demonstrated reactivity opens possibilities for further functionalization and application of Bi-Sb compounds.