Abteilung Anorganische Chemie, Institut für Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock, Germany.
Inorg Chem. 2013 May 20;52(10):6110-26. doi: 10.1021/ic400493v. Epub 2013 May 9.
The highly explosive bismuth triazide, Bi(N3)3, was obtained in pure form by the reaction of BiF3 with Me3SiN3 in acetonitrile under solvothermal conditions at temperatures between 90 and 100 °C. X-ray, (14)N NMR, infrared, and Raman spectra are discussed along with the data for the acetonitrile, acetone, and dmso adducts. The influence of the solvent on the purity of the azide products is studied in detail for Bi(N3)3 and the Bi(N3)6 ion. Moreover, temperature dependent structural dynamics in the Bi(N3)6 ion, which is caused by small changes in the local environment around the Bi(N3)6 ion in the solid state, was studied by temperature variable single crystal X-ray and Raman studies. The azido-chlorido ligand back exchange was studied in detail by NMR techniques in Bi(N3)6 and Bi(N3)3 when chlorinated solvents such as CH2Cl2 were utilized leading to the formation of CH2(N3)Cl and/or HN3 along with partially chlorinated bismuth azides.
高爆炸药三叠氮化物 Bi(N3)3 通过在 90-100°C 的溶剂热条件下，使 BiF3 与 Me3SiN3 在乙腈中反应得到。讨论了 X 射线、(14)N NMR、红外和拉曼光谱，以及乙腈、丙酮和 dmso 加合物的数据。详细研究了溶剂对 Bi(N3)3 和Bi(N3)6离子中叠氮化物产物纯度的影响。此外，通过温度变化单晶 X 射线和拉曼研究研究了Bi(N3)6离子中由于固态中Bi(N3)6离子局部环境的微小变化而引起的温度相关结构动力学。当使用氯化溶剂如 CH2Cl2 时，通过 NMR 技术详细研究了Bi(N3)6和 Bi(N3)3 中的叠氮化物-氯化物配体回交换，导致形成 CH2(N3)Cl 和/或 HN3 以及部分氯化的铋叠氮化物。
