Tetranitroacetimidic Acid: A High Oxygen Oxidizer and Potential Replacement for Ammonium Perchlorate

Considerable work has been focused on developing replacements for ammonium perchlorate (AP), a primary choice for solid rocket and missile propellants, due to environmental concerns resulting from the release of perchlorate into groundwater systems, which has been linked to thyroid cancer. Additionally, the generation of hydrochloric acid contributes to high concentrations of acid rain and to ozone layer depletion. En route to synthesizing salts that contain cationic FOX-7, a novel, high oxygen-containing oxidizer, tetranitro­acetimidic acid (TNAA), has been synthesized and fully characterized. The properties of TNAA were found to be exceptional, with a calculated specific impulse exceeding that of AP, leading to its high potential as a replacement for AP. TNAA can be synthesized easily in a one-step process by the nitration of FOX-7 in high yield (>93%). The synthesis, properties, and chemical reactivity of TNAA have been examined

1,1-Diamino-2,2-dintroethene (FOX-7) in Copper and Nickel Diamine Complexes and Copper FOX-7

1,1-Diamino-2,2-dinitroethene (FOX-7) reacts readily with copper nitrate in an aqueous solution of potassium hydroxide to form pea green Cu­(FOX)₂(H₂O)₂ (<b>5</b>). FOX-7 complexes of copper and nickel supported by a variety of diamines including Cu­(en)₂(FOX)₂(H₂O) (<b>1</b>), Cu­(pn)₂(FOX)₂ (<b>2</b>), Cu­(bipy)­(FOX)₂(H₂O)₄ (<b>3a</b>), Cu­(bipy)₂(FOX)₂(H₂O)_2.5 (<b>3b</b>), Cu­(bipy)­(FOX)₂(DMSO)₂·2DMSO (<b>3c</b>), Cu­(phen)₃(FOX)₂(H₂O)₃ (<b>4</b>), (Ni)₂(phen)₆(FOX)₄(NO₃)₃(H₂O)₂ (<b>6</b>), and Ni­(bipy)₃(FOX)₂(H₂O)₄ (<b>7a</b>) were obtained via metathesis reactions with potassium-FOX (K-FOX). Surprisingly FOX-7, in the presence of Ni­(II) and bipyridyl in a mixed solvent of methanol and dimethyl sulfoxide, gave a chelated FOX carbamate anion resulting in the compound Ni­(bipy)₂(FOX–CO₂)·(DMSO) (<b>7b</b>). All metal salts were characterized by infrared, elemental analysis, and differential scanning calorimetry (DSC). Single-crystal X-ray diffraction structures were obtained for compounds <b>1</b>,<b> 2</b>,<b> 3c</b>,<b> 6</b>, and <b>7b</b>

New Roles for 1,1-Diamino-2,2-dinitroethene (FOX-7): Halogenated FOX‑7 and Azo-bis(diahaloFOX) as Energetic Materials and Oxidizers

The syntheses and full characterization of two new halogenated 1,1-diamino-2,2-dinitroethene (FOX-7) compounds and three halogenated azo-bridged FOX-7 derivatives are described. Some of these new structures demonstrate properties that approach those of the commonly used secondary explosive RDX (cyclo-1,3,5-trimethylene-2,4,6-trinitramine). All the compounds display hypergolic properties with common hydrazine-based fuels and primary aliphatic amines (ignition delay times of 2–53 ms). This is a new role that has yet to be reported for FOX-7 and its derivatives. Their physical and energetic properties have been investigated. All compounds were characterized by single-crystal X-ray crystallography, elemental analysis, infrared spectra, and differential scanning calorimetry. These new molecules as energetic materials and hypergolic oxidizers contribute to the expansion of the chemistry of FOX-7

Energetic Salts with π‑Stacking and Hydrogen-Bonding Interactions Lead the Way to Future Energetic Materials

Among energetic materials, there are two significant challenges facing researchers: 1) to develop ionic CHNO explosives with higher densities than their parent nonionic molecules and (2) to achieve a fine balance between high detonation performance and low sensitivity. We report a surprising energetic salt, hydroxylammonium 3-dinitromethanide-1,2,4-triazolone, that exhibits exceptional properties, viz., higher density, superior detonation performance, and improved thermal, impact, and friction stabilities, then those of its precursor, 3-dinitromethyl-1,2,4-triazolone. The solid-state structure features of the new energetic salt were investigated with X-ray diffraction which showed π-stacking and hydrogen-bonding interactions that contribute to closer packing and higher density. According to the experimental results and theoretical analysis, the newly designed energetic salt also gives rise to a workable compromise in high detonation properties and desirable stabilities. These findings will enhance the future prospects for rational energetic materials design and commence a new chapter in this field

Energetic Salts with π‑Stacking and Hydrogen-Bonding Interactions Lead the Way to Future Energetic Materials

Among energetic materials, there are two significant challenges facing researchers: 1) to develop ionic CHNO explosives with higher densities than their parent nonionic molecules and (2) to achieve a fine balance between high detonation performance and low sensitivity. We report a surprising energetic salt, hydroxylammonium 3-dinitromethanide-1,2,4-triazolone, that exhibits exceptional properties, viz., higher density, superior detonation performance, and improved thermal, impact, and friction stabilities, then those of its precursor, 3-dinitromethyl-1,2,4-triazolone. The solid-state structure features of the new energetic salt were investigated with X-ray diffraction which showed π-stacking and hydrogen-bonding interactions that contribute to closer packing and higher density. According to the experimental results and theoretical analysis, the newly designed energetic salt also gives rise to a workable compromise in high detonation properties and desirable stabilities. These findings will enhance the future prospects for rational energetic materials design and commence a new chapter in this field

New Roles for 1,1-Diamino-2,2-dinitroethene (FOX-7): Halogenated FOX‑7 and Azo-bis(diahaloFOX) as Energetic Materials and Oxidizers

The syntheses and full characterization of two new halogenated 1,1-diamino-2,2-dinitroethene (FOX-7) compounds and three halogenated azo-bridged FOX-7 derivatives are described. Some of these new structures demonstrate properties that approach those of the commonly used secondary explosive RDX (cyclo-1,3,5-trimethylene-2,4,6-trinitramine). All the compounds display hypergolic properties with common hydrazine-based fuels and primary aliphatic amines (ignition delay times of 2–53 ms). This is a new role that has yet to be reported for FOX-7 and its derivatives. Their physical and energetic properties have been investigated. All compounds were characterized by single-crystal X-ray crystallography, elemental analysis, infrared spectra, and differential scanning calorimetry. These new molecules as energetic materials and hypergolic oxidizers contribute to the expansion of the chemistry of FOX-7