Novel High-Energy Density Materials. Synthesis and Characterization of Triazidocarbenium Dinitramide, -Perchlorate, and -Tetrafluoroborate

• Published in: Journal of the American Chemical Society Vol. 119; no. 38; pp. 8802 - 8808
• Main Authors: Petrie, Mark A, Sheehy, Jeffrey A, Boatz, Jerry A, Rasul, Golam, Surya Prakash, G. K, Olah, George A, Christe, Karl O
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 24.09.1997; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja9714189

The triazidocarbenium cation, C(N3)3 +, was successfully combined with the energetic N(NO2)2 - and ClO4 - anions in the form of highly energetic salts. The new C(N3)3 +BF4 - salt was also prepared, and all compounds were characterized by their material balances and vibrational spectroscopy. Electronic structure calculations were carried out for C(N3)3 + at the B3LYP/6-31G*, B3LYP/cc-pVDZ, B3LYP/cc-pVTZ, and HF/cc-pVDZ levels of theory. At all levels, the energy minimum is the planar C 3 h structure, and the vibrational spectra were assigned and analyzed for this structure. The heats of formation of C(N3)3 +N(NO2)2 - and C(N3)3 +ClO4 - were estimated to be endothermic by 252 and 218 kcal mol-1 and explain the high explosive power of these salts.