Syntheses, Structure, and Reactivity of Amino(azido)stibanes

Amino(azido)stibanes Mes*N(SiMe 3 )Sb(N 3 )X (X = N 3 , 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(SiMe 3 )Sb(OTf)X species (X = Cl, N 3 , and OTf; OTf = triflate = CF 3 SO 3 – ) are labile with respect to Me 3 Si–OTf elimination even at ambient temperatures and form in situ the highly reactive iminostibane Mes*N=SbX, which rapidly decomposes. Diazide Mes*N(SiMe 3 )Sb(N 3 ) 2 slowly decomposes when a Lewis acid such as B(C 6 F 5 ) 3 is present, thus leading to the formation of a salt that bears a heterocyclic Sb–N dication and an [N 3 –B(C 6 F 5 ) 3 ] – adduct anion in good yields.