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Energetic Hydrazine‐Based Salts with Nitrogen‐Rich and Oxidizing Anions
Author(s) -
Sabaté Carles Miró,
Delalu Henri,
Jeanneau Erwann
Publication year - 2012
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201200437
Subject(s) - chemistry , iodide , oxidizing agent , salt (chemistry) , perchlorate , medicinal chemistry , infrared spectroscopy , raman spectroscopy , inorganic chemistry , nitrogen , nuclear chemistry , ion , organic chemistry , physics , optics
1,1,1‐Trimethylhydrazinium iodide ([(CH 3 ) 3 NNH 2 ]I, 1 ) was reacted with a silver salt to form the corresponding nitrate ([(CH 3 ) 3 NNH 2 ][NO 3 ], 2 ), perchlorate ([(CH 3 ) 3 NNH 2 ][ClO 4 ], 3 ), azide ([(CH 3 ) 3 NNH 2 ][N 3 ], 4 ), 5‐amino‐1 H ‐tetrazolate ([(CH 3 ) 3 NNH 2 ][H 2 NCN 4 ], 5 ), and sulfate ([(CH 3 ) 3 NNH 2 ] 2 [SO 4 ]⋅2H 2 O, 6 ⋅2H 2 O) salts. The metathesis reaction of compound 6 ⋅2H 2 O with barium salts led to the formation of the corresponding picrate ([(CH 3 ) 3 NNH 2 ][(NO 2 ) 3 Ph ‐ O], 7 ), dinitramide ([(CH 3 ) 3 NNH 2 ][N(NO 2 ) 2 ], 8 ), 5‐nitrotetrazolate ([(CH 3 ) 3 NNH 2 ][O 2 NCN 4 ], 9 ), and nitroformiate ([(CH 3 ) 3 NNH 2 ][C(NO 2 ) 3 ], 10 ) salts. Compounds 1 – 10 were characterized by elemental analysis, mass spectrometry, infrared/Raman spectroscopy, and multinuclear NMR spectroscopy ( 1 H, 13 C, and 15 N). Additionally, compounds 1 , 6 , and 7 were also characterized by low‐temperature X‐ray diffraction techniques (XRD). Ba(NH 4 )(NT) 3 (NT=5‐nitrotetrazole anion) was accidentally obtained during the synthesis of the 5‐nitrotetrazole salt 9 and was also characterized by low‐temperature XRD. Furthermore, the structure of the [(CH 3 ) 3 NNH 2 ] + cation was optimized using the B3LYP method and used to calculate its vibrational frequencies, NBO charges, and electronic energy. Differential scanning calorimetry (DSC) was used to assess the thermal stabilities of salts 2 – 5 and 7 – 10 , and the sensitivities of the materials towards classical stimuli were estimated by submitting the compounds to standard (BAM) tests. Lastly, we computed the performance parameters (detonation pressures/velocities and specific impulses) and the decomposition gases of compounds 2 – 5 and 7 – 10 and those of their oxygen‐balanced mixtures with an oxidizer.