Ralf Haiges - Green energetic materials: Binary group 15 polyazides.

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      Publication Details (including relevant citation   information): Haiges, Ralf, Christe, Karl O., Rahm,   Martin, Dixon, David A., Abstracts of Papers, 243rd ACS   National Meeting & Exposition, San Diego, CA, United States,   March 25-29, 2012, 2012, pp INOR-51

      Abstract: Polyazides are highly endothermic   compds. that have great potential as energetic materials. For   example, lead diazide is widely used as primary explosive. The   low toxicity and environmentally benign character of bismuth   renders it an ideal replacement for lead in this application. As   a consequence, we have systematically studied the synthesis and   characterization of binary bismuth and related group 15   polyazides. The binary group 15 polyazides, As(N3)3, Sb(N3)3 and   Bi(N3)3 were prepd. and stabilized by either anion or   donor-acceptor adduct formation. Crystal structures are reported   for [Bi(N3)4]-, [Bi(N3)5]2-, [bipyBi(N3)5]2-, [Bi(N3)6]3-,   bipyAs(N3)3, bipySb(N3)3 and [(bipy)2Bi(N3)3]2. An interesting   feature of these pnicogen(+III) compds. is the presence of a free   valence electron pair on the central atom. The [Bi(N3)5]2- anion   possesses a sterically active, free, Bi valence electron pair and   a monomeric, pseudo-octahedral structure with CN 6, while its   bipyridyl adduct has a pseudo-monocapped trigonal prismatic   structure with CN 7 and a sterically inactive free valence   electron pair. Attempts to grow single crystals of polymeric,   free Bi(N3)3 were unsuccessful. However, the crystal structure of   its bis-bipyridyl adduct, [(bipy)2Bi(N3)3]2, was successfully   detd. It is dimeric and made up from two square BiN8 antiprisms,   with Bi having CN 8 and a sterically inactive, free valence   electron pair, and sharing an edge consisting of two   μ1,1-bridging N3 ligands. The novel bipyAs(N3)3 and bipySb(N3)3   adducts were also prepd. and structurally characterized. They are   monomeric, isostructural and contain a sterically active, free   valence electron pair on their central atom and a coordination   no. of 6. [on SciFinder(R)]

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