title: Binary pnictogen azides--an experimental and theoretical study: [As(N3)4]-, [Sb(N3)4]-, and [Bi(N3)5(dmso)]2-.
abstract: [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)](2)[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))](4) (E=As, Sb) and pentaazidobismuthate, stabilized as the dimethyl sulfoxide (DMSO) anion adduct, [PPh(4)](2)[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.
authors.affiliation: Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany. axel.schulz@uni-rostock.de
authors.forename: Axel
authors.initials: A
authors.lastname: Schulz
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger