Abstract

AbstractAmino(azido)stibanes Mes*N(SiMe3)Sb(N3)X (X = N3, Cl, OTf) were synthesized and fully characterized. Their structures were determined by single‐crystal X‐ray diffraction and are rare examples of antimony azides. On account of weak Sb···X van der Waals interactions, centrosymmetric dimers are observed in the solid state. Mes*N(SiMe3)Sb(OTf)X species (X = Cl, N3, and OTf; OTf = triflate = CF3SO3–) are labile with respect to Me3Si–OTf elimination even at ambient temperatures and form in situ the highly reactive iminostibane Mes*N=SbX, which rapidly decomposes. Diazide Mes*N(SiMe3)Sb(N3)2 slowly decomposes when a Lewis acid such as B(C6F5)3 is present, thus leading to the formation of a salt that bears a heterocyclic Sb–N dication and an [N3–B(C6F5)3]– adduct anion in good yields.

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