Regioselective bisaddition of M3N@Ih-C80 (M = Y, Gd) was observed for the first time in the Prato reaction with N-ethylglycine and formaldehyde. The main kinetic bisadduct of Y3N@C80 was determined to be a [6,6],[6,6] adduct by (1)H and (13)C NMR and vis/NIR spectroscopy, and it converted to a mixture of regioisomers upon heating via a sigmatropic rearrangement. The main kinetic bisadduct of Gd3N@C80 (the [6,6],[6,6] adduct on the basis of vis/NIR data) existed stably under thermal conditions without isomerization. The likely position of the second addition of the Gd3N@C80 bisadduct was predicted by DFT calculations.

Three isomeric dinitropyrazoles (DNPs) were synthesized starting from readily available 1H‐pyrazole by slightly improved methods than described in the literature. 3,4‐Dinitropyrazole (3), 1,3‐dinitropyrazole (4), and 3,5‐dinitropyrazole (5) were obtained and compared to each other with respect to thermal stability, crystallography, sensitivity and energetic performance. Two isomers (3 and 4) show high densities (1.79 and 1.76 g cm–3) and interesting thermal behavior as melt‐castable materials (3: Tmelt.=71 °C, Tdec.=285 °C; 5: Tmelt. = 68 °C, Tdec.=171 °C). Furthermore, eight salts (sodium, potassium, ammonium, hydrazinium, hydroxylammonium, guanidinium, aminoguanidinium and 3,6,7‐triamino‐[1,2,4]triazolo[4,3‐b][1,2,4]triazole (TATOT) of 3 and 5 were synthesized in order to tune performance and sensitivity values. These compounds were characterized using 1H, 13C, 14N, 15N NMR and IR spectroscopy as well as mass spectrometry, elemental analysis and thermal analysis through differential scanning calorimetry. Crystal structures of 14 compounds were obtained (3–7, 10–12 and 15–20) by low‐temperature single crystal X‐ray diffraction. Impact, friction and electrostatic discharge (ESD) values were also determined by standard methods. The sensitivity values range between 8.5 and 40 J for impact and 240 N and 360 N for friction and show mainly insensitive character. The energetic performances were determined using recalculated X‐ray densities, heats of formation and the EXPLO5 code and support the energetic character of the title compounds. The calculated energetic performances (VD: 6245–8610 m s−1; pCJ: 14.1–30.8 GPa) were compared to RDX ((O2NNCH2)3).

Potassium 1,1'-dinitramino-5,5'-bitetrazolate is one of the most promising primary explosives which is currently under investigation for different applications. This is due to its high initiation power and the exclusion of heavy metals. To close the gap, the remaining alkali metal salts such as the lithium 6, sodium 7, rubidium 8 and cesium 9 salts were synthesized by reaction of the highly soluble ammonium salt 5 with its corresponding metal hydroxide solutions. In addition, the highly explosive silver salt 10 as well as several other transition metal(ii) amine complexes with nickel(ii) 11, copper(ii) 12 and zinc(ii) 13 were prepared in a similar manner. The structure of all compounds was determined by X-ray diffraction. The sensitivities toward impact, friction, heat and electrostatic discharge as well as their behavior on laser irradiation of the transition metal complexes were explored.

The syntheses of two different isomeric dinitropyrazole N-oxides are described and compared to each other. 3,4-Dinitropyrazole-1N-oxide (2) and 3,5-dinitropyrazole-1N-oxide (4) were used, and four different nitrogen-rich salts were synthesized in order to enhance performance and sensitivity values. Furthermore, two methylene-bridged isomeric dinitropyrazoles were synthesized by using diiodomethane. The obtained compounds were characterized by using low-temperature single-crystal X-ray diffraction, IR spectroscopy, multinuclear NMR spectroscopy, mass spectrometry, elemental analysis and DSC measurements. The bridged compounds show a high thermal stability (T dec. : 319°C and 330°C) whereas the ionic compounds [a] 4125 Scheme 1. Synthesis of bis(3,5-dinitro-pyrazol-1-yl)methane (1), bis(3,4-dinitro-pyrazol-1-yl)methane (3), 3,4-dinitropyrazol-1-oxide (2) and 3,5-dinitropyrazol-1-oxide (4) as well as the ionic derivatives of 2 and 4.

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