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Nitrogen-Rich Salts Based on the Energetic 5,5′-(Hydrazine-1,2-diyl)bis[1H-tetrazolide] Anion

✍ Scribed by Moritz Eberspächer; Thomas M. Klapötke; Carles Miró Sabaté

Publisher
John Wiley and Sons
Year
2009
Tongue
German
Weight
473 KB
Volume
92
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

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The reaction of 5,5′‐(hydrazine‐1,2‐diyl)bis[1__H__‐tetrazole] (HBT) with N‐bases yielded a new family of energetic N‐rich salts based on the 5,5′‐(hydrazine‐1,2‐diyl)bis[1__H__‐tetrazol‐1‐ide] anion with ammonium (see 1), hydrazinium (see 2), guanidinium (see 3), and aminoguanidinium (see 4) cations (5,5′‐(hydrazine‐1,2‐diyl)bis[1__H__‐tetrazol‐1‐ide]=5,5′‐(hydrazine‐1,2‐diyl)bis[tetrazolate]). All compounds were characterized by analytical and spectroscopic methods, and the crystal structure of 1 was determined by X‐ray analysis (triclinic, P$\bar 1$). (Carboxyamino)guanidine betaine monohydrate (=2‐(aminoiminomethyl)hydrazinecarboxylic acid hydrate (1 : 1); 5) was obtained as a by‐product in the synthesis of 4 and was characterized by X‐ray analysis (monoclinic, P__2~1~/__c). Differential‐scanning calorimetric (DSC) measurements were used to assess the thermal behavior of the energetic salts 1–4, and bomb calorimetry allowed us to determine the experimental constant‐volume energies of formation $\rm{(\Delta _{\rm{c}} U_{\exp} )}$. In addition, the detonation parameters (pressure and velocity) were calculated from the energies of formation (back‐calculated from $\rm{\Delta _{\rm{c}} U_{\exp} }$) with the EXPLO5 code, and their validity was checked by comparison with the results obtained from theoretical constant‐volume energies of formation $\rm{(\Delta _{\rm{c}} U_{{\rm{pred}}} )}$ obtained by means of quantum‐chemical calculation (MP2) of electronic energies and an approximation of lattice enthalpy. Lastly, the sensitivity to shock, friction, and electrostatic discharge of 1–4 was measured by submitting the compounds to standard tests, and the ICT code was used to predict the products formed upon decomposition of the salts.

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## Abstract From the two nitrogen‐rich ligands BT^2−^ (BT=5,5′‐bitetrazole) and BTT^3−^ (BTT=1,3‐bis(1__H__‐tetrazol‐5‐yl)triazene), a series of novel rare earth metal complexes were synthesised. For the BT ligand, a vast number of these complexes could be structurally characterised by single‐cryst