Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany.
Chemistry. 2012 Mar 5;18(10):2902-11. doi: 10.1002/chem.201102656. Epub 2012 Feb 15.
[PPh(4)][EI(4)] (E=As, Sb, Bi) salts were reacted with four and five equivalents of AgN(3) to form tetraazidopnictates and pentaazidopnictates of the type [PPh(4)][E(N(3))(4)] and PPh(4)[E(N(3))(5)], respectively. The synthesis of [PPh(4)][P(N(3))(4)] was also attempted from the reaction of P(N(3))(3) with [PPh(4)]N(3), but it yielded only the starting materials. Herein, we report the synthesis and structure elucidation of [PPh(4)]E(N(3)) (E=As, Sb) and pentaazidobismuthate, stabilized as the dimethyl sulfoxide (DMSO) anion adduct, PPh(4)[Bi(N(3))(5)(dmso)]. Successive anion formation along the series E(N(3))(3)+nN(3)(-) (n=1-3) and E(N(3))(5)+N(3)(-) was studied by density functional theory.
[PPh(4)][EI(4)]（E=As、Sb、Bi）盐与四当量和五当量的 AgN(3)反应，分别形成四氮杂取代物和五氮杂取代物，其结构为[PPh(4)][E(N(3))(4)]和PPh(4)[E(N(3))(5)]。我们还尝试从 P(N(3))(3)与[PPh(4)]N(3)的反应中合成[PPh(4)][P(N(3))(4)]，但只得到了起始原料。在此，我们报告了[PPh(4)]E(N(3))（E=As、Sb）和五氮合锑酸根的合成和结构阐明，其作为二甲基亚砜（DMSO）阴离子加合物稳定，即PPh(4)[Bi(N(3))(5)(dmso)]。通过密度泛函理论研究了 E(N(3))(3)+nN(3)(-)（n=1-3）和 E(N(3))(5)+N(3)(-)系列中连续阴离子形成的情况。
