title: Energetic 2,2-Dimethyltriazanium Salts: A New Family of Nitrogen-Rich Hydrazine Derivatives.
abstract: Amination of 1,1-dimethylhydrazine with NH2 Cl or hydroxylamine-O-sulfonic acid yields 2,2-dimethyltriazanium (DMTZ) chloride (3) and sulphate (4), respectively. The DMTZ cation was paired with the nitrogen-rich anions 5-aminotetrazolate (5), 5-nitrotetrazolate (6), 5,5'-azobistetrazolate (7), and azide (8), yielding a new family of energetic salts. The synthesis was carried out by metathesis reactions of salts 3 or 4 and a suitable silver or barium salt. To minimize the risks involved when using heavy metal salts, we used electrodialysis for the synthesis of azide 8, which avoids the use of highly sensitive species. The DMTZ derivatives were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, and X-ray diffraction. Thermal stabilities were measured using DSC analysis and their sensitivities towards classical stimuli were determined using standard tests. Lastly, the relationship between hydrogen bonding in the solid state and sensitivity is discussed.
authors.affiliation: Laboratoire Hydrazines et Composés Energétiques Polyazotés UMR 5278, UCBL/CNRS/CNES/Herakles (Safran), 22 Ave. Gaston Berger, 69622, Villeurbanne, France.
authors.forename: Valérian
authors.initials: V
authors.lastname: Forquet
authors.affiliation: Laboratoire Hydrazines et Composés Energétiques Polyazotés UMR 5278, UCBL/CNRS/CNES/Herakles (Safran), 22 Ave. Gaston Berger, 69622, Villeurbanne, France. carlos.miro-sabate@univ-lyon1.fr.
authors.forename: Carlos Miró
authors.initials: CM
authors.lastname: Sabaté
authors.affiliation: Direction Recherche et Technologie, Herakles (Safran), Centre de Recherches du Bouchet, 9 rue Lavoisier, 91710, Vert-Le-Petit, France.
authors.forename: Guy
authors.initials: G
authors.lastname: Jacob
authors.affiliation: CNES, Direction des Lanceurs, SDT Equipements Propulsifs et Mécanismes, 52 rue Jacques Hillairet, 75012, Paris, France.
authors.forename: Yann
authors.initials: Y
authors.lastname: Guelou
authors.affiliation: Laboratoire Hydrazines et Composés Energétiques Polyazotés UMR 5278, UCBL/CNRS/CNES/Herakles (Safran), 22 Ave. Gaston Berger, 69622, Villeurbanne, France.
authors.forename: Henri
authors.initials: H
authors.lastname: Delalu
authors.affiliation: Laboratoire Hydrazines et Composés Energétiques Polyazotés UMR 5278, UCBL/CNRS/CNES/Herakles (Safran), 22 Ave. Gaston Berger, 69622, Villeurbanne, France. chaza.darwich@univ-lyon1.fr.
authors.forename: Chaza
authors.initials: C
authors.lastname: Darwich
keywords: X-ray crystal structure; electrodialysis; energetic materials; heterocycles; triazanium salts