Ralf Haiges - Binary Group 15 Polyazides. Structural Characterization of [Bi(N3)4]-, [Bi(N3)5]2-, [bipy·Bi(N3)5]2-, [Bi(N3)6]3-, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons.

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      Publication Details (including relevant citation   information): Haiges, Ralf, Rahm, Martin, Dixon, David   A., Garner, Edward B., Christe, Karl O., Inorg. Chem.,   2012, 51 (2), pp 1127-1141

      Abstract: The binary Group 15 polyazides   As(N3)3, Sb(N3)3, and Bi(N3)3 were stabilized by either anion or   donor-acceptor adduct formation. Crystal structures are reported   for [Bi(N3)4]-, [Bi(N3)5]2-, [bipy·Bi(N3)5]2-, [Bi(N3)6]3-,   bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2. The lone   valence electron pair on the central atom of these   pnictogen(+III) compds. can be either sterically active or   inactive. The [Bi(N3)5]2- anion possesses a sterically active   lone pair and a monomeric pseudo-octahedral structure with a   coordination no. of 6, whereas its 2,2'-bipyridine adduct   exhibits a pseudo-monocapped trigonal prismatic structure with CN   7 and a sterically inactive lone pair. Because of the high   oxidizing power of Bi(+V), reactions aimed at Bi(N3)5 and   [Bi(N3)6]- resulted in the redn. to bismuth(+III) compds. by   [N3]-. The powder x-ray diffraction pattern of Bi(N3)3 was   recorded at 298 K and is distinct from that calcd. for Sb(N3)3   from its single-crystal data at 223 K. The [(bipy)2·Bi(N3)3]2   adduct is dimeric and derived from two BiN8 square antiprisms   sharing an edge consisting of two μ1,1-bridging N3 ligands and   with bismuth having CN 8 and a sterically inactive lone pair. The   novel bipy·As(N3)3 and bipy·Sb(N3)3 adducts are monomeric and   isostructural and contain a sterically active lone pair on their   central atom and a CN of 6. A systematic quantum chem. anal. of   the structures of these polyazides suggests that the M06-2X d.   functional is well suited for the prediction of the steric   activity of lone pairs in main-group chem. Also, the solid-state   structures can strongly differ from those of the free gas-phase   species or those in solns. and lone pairs that are sterically   inactive in a chem. surrounding can become activated in the free   isolated species. [on SciFinder(R)]

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