Binary Pnictogen Azides—An Experimental and Theoretical Study: [As(N3)4]−, [Sb(N3)4]−, and [Bi(N3)5(dmso)]2− |
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| Authors: | Prof. Dr. Axel Schulz Dr. Alexander Villinger |
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| Affiliation: | 1. Institut für Chemie, Universit?t Rostock, Albert‐Einstein‐Str. 3a, 18059 Rostock (Germany), Fax: (49+)?0381‐498‐6382;2. Leibniz‐Institut für Katalyse e.V. Rostock, Albert‐Einstein‐Str. 29a, 18059 Rostock (Germany) |
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| Abstract: | [PPh4][EI4] (E=As, Sb, Bi) salts were reacted with four and five equivalents of AgN3 to form tetraazidopnictates and pentaazidopnictates of the type [PPh4][E(N3)4] and [PPh4]2[E(N3)5], respectively. The synthesis of [PPh4][P(N3)4] was also attempted from the reaction of P(N3)3 with [PPh4]N3, but it yielded only the starting materials. Herein, we report the synthesis and structure elucidation of [PPh4][E(N3)]4 (E=As, Sb) and pentaazidobismuthate, stabilized as the dimethyl sulfoxide (DMSO) anion adduct, [PPh4]2[Bi(N3)5(dmso)]. Successive anion formation along the series E(N3)3+nN3? (n=1–3) and E(N3)5+N3? was studied by density functional theory. |
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| Keywords: | arsenic azides bismuth pnictogen thermochemistry |
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