1‐Amino‐5‐methyltetrazole in Energetic 3 d Transition Metal Complexes – Ligand Design for Future Primary Explosives

Abstract

New lead‐free primary explosives are needed for safe future ignition and initiation applications. Especially, ignition by low‐energy laser irradiation has been demonstrated to be a valuable method. For this technology, primary explosives with safer sensitivities are needed. In order to adjust the desired properties of the neat primary explosives, we follow the concept of “energetic coordination compounds” (ECC) in which the ligand significantly alters the final properties. As the result of a study where 1‐amino‐5H‐tetrazole (1‐AT) was used as one of the most endothermic ligands, yielding materials with outstanding performance but very high sensitivities, in this work its 5‐methyl analogue 1‐amino‐5‐methyltetrazole (1‐AMT, 1) was synthesized and applied as ligand. For a short evaluation, metal perchlorate complexes [M(1‐AMT)6](ClO4)2 of manganese(II), iron(II), and zinc(II) as well as [Cu(1‐AMT)4(H2O)](ClO4)2 were prepared. All compounds were intensively characterized e. g., by XRD, IR, EA, TGA, DTA as well as sensitivity measurements (impact, friction, BDIS, and ESD). The obtained materials show reduced performance but they are safer to handle than the corresponding 1‐AT derivatives. Moreover, the satisfactory performances of ECC 3 and 4 were impressively demonstrated by PETN initiation and laser ignition experiments.

Hybridization of Dinitramide and Dicyanamide: Evaluation of Nitrocyanamide in Energetic Salts and Coordination Compounds

“…In the case of pure silver nitrocyanamide ( 5a ), these results are not surprising, as the compound is described as sensitive, but no BAM sensitivities were reported . Similar findings apply to complexes based on the AMT ligand. , For example, [Cu­(AMT) 4 (H 2 O)]­(DN) 2 , which also has a pyramidal structure and has an aqua ligand instead of coordinating anions, is extremely sensitive to IS and FS (IS = 2 J, FS = 3 N) . In this context, the low impact sensitivity of 12c is no longer surprising.…”

4,5-Dicyano-1,2,3-Triazole—A Promising Precursor for a New Family of Energetic Compounds and Its Nitrogen-Rich Derivatives: Synthesis and Crystal Structures

“…2-methyl-4,5-dicarboxylic acid dimethyl ester-1,2,3-Triazole ( 14) was prepared from 13 by esterification in 82% yield. On the one hand, compound 11 could to be hydrolyzed under acidic condition to gain 1-methyl-4,5-dicarboxamide-1,2,3-triazole (12) in 62% yield; on the other hand, 14 and concentrated aqueous ammonia reacted for 12 h to produce compound 12. 2-methyl-4,5-dicarbohydrazide-1,2,3-triazole (15) and 2-methyl-4,7-dione-1,2,3-triazolo [4,5-d]pyridazine (16) were synthesized according to the previous method which was introduced in Scheme 5.…”

“…However, only few studies of 1,2,3-triazoles derivatives are reported in the field of energetic materials. At present, the research of energetic materials are concentrate on nitrogen-rich heterocyclic compounds which are furazan [6][7][8], 1,2,4-triazole [9][10][11], and tetrazole [12][13][14]. However, 1,2,3-triazole is a surprisingly stable structure compared to other organic compounds with three contiguous nitrogen atoms [15].…”

Alkaline metal and alkaline earth metal salts of di(1H-tetrazol-5-yl)methanone (DTO): energetic catalysts for ammonium perchlorate decomposition

“…Therefore, a large number of complexes based on tetrazole ligands were prepared, with their excellent properties providing brilliant application prospects in aerospace and the military domains. [5][6][7][8][9][10] Compared with monotetrazole compounds, bicyclotetrazole compounds have more modification sites, which can be more flexible to achieve adjustable performance as needed. The introduction of bridging blocks such as imino, 11 azo, 12 methylene, [13][14][15] oxime, and hydrazine groups 16,17 effectively combines two or more tetrazolyl components.…”