This comprehensive study features the synthesis, characterization and evaluation of new energetic coordination compounds (ECC) based on two of the most powerful neutral tetrazoles, which have great potential as lead-free primary explosives.

Energetic coordination compounds (ECC) based on 3d or 4d transition metals show promising characteristics to be used as potential replacements for highly toxic leadcontaining primary explosives. Herein we report the synthesis of 12 new ECC based on 1-azidoethyl-5H-tetrazole (AET) or 1-ethyl-5H-tetrazole (1-ETZ) as nitrogen-rich ligandsa s well as variousc entral metals (Cu 2 + ,F e 2 + ,Z n 2 + ,A g + )a nd anions such as perchlorate and nitrate. The influence of the increased endothermicity by adding an additional azide group was studied by comparing analogous ECC based on AET and 1-ETZ. Furthermore, the compounds were extensively analyzed by XRD, IR, EA, solid-state UV/Vis,a nd DTAa s well as their sensitivities toward impactand friction were determined with BAM standard techniques, together with their sensitivity against electrostatic discharge. The sensitivities were compared with the one toward ball drop impact measurements. Classicali nitiation tests (nitropenta filled detonators) and ignitionbylaser irradiation highly prove the potential use of the most promising compounds in lead-freei nitiation systems.[a] M.

A concept for stabilizing highly sensitive and explosive copper(II) azide with 1‐N‐substituted tetrazoles is described. It was possible to stabilize the system by the use of highly endothermic, nitrogen‐rich ligands. The sensitivities of the resulting energetic copper coordination compounds can be tuned further by variation of the alkyl chain of the ligands and by phlegmatization of the complexes with classical additives during the synthesis. It is demonstrated, using the compound based on 1‐methyl‐5H‐tetrazole ([Cu(N3)2(MTZ)], 1) that this class of complexes can be applied as a potential replacement for both lead azide (LA) and lead styphnate (LS). The complex was extensively investigated according to its chemical (elemental analysis, single‐crystal and powder X‐ray diffraction, IR spectroscopy, scanning electron microscopy) and physico‐chemical properties (differential thermal analysis, sensitivities towards impact, friction, and electrostatic discharge) compared to pure copper(II) azide.

1- and 2-Nitratoethyl-5H-tetrazole (1-NET, 2-NET) were prepared through nitration of the respective alkyl alcohol using 100% nitric acid. A mixture of 1- and 2-hydroxyethyl-5H-tetrazole was obtained after alkylation of 1,5H-tetrazole....

This study shows the fine-tuning adjustment of copper(ii) complexes by trinitrophenolates and different N-aminotetrazole ligands to applicable highly energetic materials.