A Smart Access to the Dinitramide Anion – The Use of Dinitraminic Acid for the Preparation of Nitrogen‐Rich Energetic Copper(II) Complexes. Issue 35 (10th June 2021)

• Record Type: Journal Article
• Authors: Gruhne, Michael S.; Wurzenberger, Maximilian H. H.; Lommel, Marcus; Stierstorfer, Jörg
• Is Part Of: Chemistry. Volume 27:Issue 35(2021)
• Page Start: 9112
• Page End: 9123
• Publication Date: 2021-06-10
• Subjects: burn rate catalyst -- dinitramide -- dinitraminic acid -- laser ignition -- primary explosives; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202100747
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Dinitraminic acid (HN(NO2 )2, HDN) was prepared by ion exchange chromatography and acid‐base reaction with basic copper(II) carbonate allowed the in situ preparation of copper(II) dinitramide, which was reacted with twelve nitrogen‐rich ligands, for example, 4‐amino‐1, 2, 4‐triazole, 1‐methyl‐5 H ‐tetrazole, di(5 H ‐tetrazolyl)‐methane/‐ethane/‐propane/‐butane. Nine of the complexes were investigated by low‐temperature X‐ray diffraction. In addition, all compounds were investigated by infrared spectroscopy (IR), differential thermal analysis (DTA), elemental analysis (EA) and thermogravimetric analysis (TGA) for selected compounds. Furthermore, investigations of the materials were carried out regarding their sensitivity toward impact (IS), friction (FS), ball drop impact (BDIS) and electrostatic discharge (ESD). In addition, hot plate and hot needle tests were performed. Complex [Cu(AMT)4 (H2 O)](DN)2, based on 1‐amino‐5‐methyltetrazole (AMT), is most outstanding for its detonative behavior and thus also capable of initiating PETN in classical initiation experiments. Laser ignition experiments at a wavelength of 915 nm were performed for all substances and solid‐state UV‐Vis spectra were recorded to apprehend the ignition mechanism. Abstract : The dinitramide anion was made accessible for complexation through the use of dinitraminic acid and basic copper(II) carbonate. The in situ prepared copper dinitramide was complexed by 13 different highly endothermic tri‐ and tetrazole ligands. By the choice of ligand, complexes were obtained that possess thermal stability exceeding 200 degrees Celsius, one even capable of initiating pentaerythritol tetranitrate (PETN). The examined compounds were successfully ignited in laser experiments, with one complex even detonating.