Why does the cyclic pentazolate anion fail to undergo <i>N</i>-oxidization in oxone solution?

Xu, Zhihong; Jiang, Shuaijie; Hou, Tianyang; Zhang, Xiaopeng; Lu, Ming; Xu, Yuangang

doi:10.1039/d3nj00215b

Cited by 3 publications

(3 citation statements)

References 29 publications

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“…Nitrogen-rich energetic materials (NREMs) represent an important type of high-energy-density materials (HEDMs), in the view of the significant energy release from the bond-breaking energies between bonded nitrogen [1][2][3][4]. A well-accepted principle to design NREMs for enhancing their at room temperature [9].…”

Section: Introductionmentioning

confidence: 99%

A molecular dynamics simulation study of thermal transport in hydrazinium cyclo-pentazolate

Xiong,

Xu,

Jia

2024

J. Phys.: Condens. Matter

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Cyclo-pentazolate salts (CPSs) as a new type of high-energy-density materials (HEDMs) with high nitrogen content have attracted considerable research attention. In contrast to the extensive studies on their energy properties, the thermal transport process in CPSs has been less studied which relates closely to the thermal safety of this material. Concerning the hydrazinium cyclo-pentazolate (HCP), we conduct a computational study to estimate the thermal conductivity of HCP by means of the non-equilibrium molecular dynamics (NEMD) simulation. To achieve that, we have customized interaction parameters based on the default OPLS force field for the HCP, as benchmarked by its crystal structure. Our simulations have revealed surprisingly anisotropic thermal conductivity for the HCP, while the thermal conductivity becomes highest roughly in the direction perpendicular to cyclo-N5 - with its value notably higher than common high explosives. By modulating the interaction parameters within the HCP molecule, we have further captured a dominant role of the interaction between cyclo-N5 - in regulating the thermal conductivity of the HCP. The attractive Lennard-Jones (LJ) potential may restrict the relative motion between cyclo-N5 -, which forms a long-range order thus enhances thermal transport in the direction perpendicular to cyclo-N5 -. Our simulation result on the effect of (cyclo-N5 -)-(cyclo-N5 -) interaction provide insights to engineer thermal transport in CPSs at the molecular level.

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Section: Introductionmentioning

confidence: 99%

A molecular dynamics simulation study of thermal transport in hydrazinium cyclo-pentazolate

Xiong,

Xu,

Jia

2024

J. Phys.: Condens. Matter

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“…But they failed to obtain the expected nitrogen oxides owing to the high energy barrier of the involved reaction, which resulted in the decomposition of the ring at the required high temperature. [14] Overall, no pure single-ring pentazolyl derivative based on covalent bond has been successfully isolated so far. Although several researchers have reported calculations related to some pentazolyl derivatives in recent years, such as cyclo-N 5 -F, N-oxide pentazolate materials, and aminopentazole derivatives, the stability of single-ring pentazolate rings with various functional groups remains obscure.…”

Section: Introductionmentioning

confidence: 99%

“…attempted to oxidize cyclo ‐N 5 − using an oxone solution. But they failed to obtain the expected nitrogen oxides owing to the high energy barrier of the involved reaction, which resulted in the decomposition of the ring at the required high temperature [14] . Overall, no pure single‐ring pentazolyl derivative based on covalent bond has been successfully isolated so far.…”

Section: Introductionmentioning

confidence: 99%

Insight into the Stability of Pentazolyl Derivatives based on Covalent Bond

Jiang,

Xia,

Zhang

et al. 2024

ChemPhysChem

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Pentazole is regarded as a unique inorganic molecule that possess organic heterocyclic structure. Therefore, the research on pentazolyl derivatives represents a cutting‐edge direction in both contemporary inorganic chemistry and heterocyclic chemistry. Moreover, their synthesis is regarded as the most significant research topic in the field of energetic materials due to the great potential of pentazolyl derivatives to breakthrough the energy bottleneck of CHNO‐based energetic materials. However, synthesizing pentazolyl derivatives is challenging. To provide a theoretical support for the synthesis, we conducted theoretical studies on six single‐ring pentazolyl derivatives with different functional groups. The results suggest that derivatization reduces the bond strength and weakens the aromaticity of the pentazolate ring. Further analysis showed that derivatization mainly affects the π aromaticity of the pentazolate ring, and ultimately causing poor stability of the pentazolyl derivatives. Among the six derivatives investigated in this study, fluoro pentazole (cyclo‐N5‐F) and hydroxyl pentazole (cyclo‐N5‐OH) possess good aromaticity, which is similar to the reported cyclo‐N5‐NCHN(CH3)2. Further calculations show that the kinetic stability of cyclo‐N5‐OH is higher than that of cyclo‐N5‐F. These results collectively indicate that cyclo‐N5‐OH is a promising candidate for synthesizing single‐ring pentazolyl derivatives.

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Experimental detection of the diamino-pentazolium cation and theoretical exploration of derived high energy materials

Hou,

Yuan,

Jiang

et al. 2024

Sci Rep

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In this work, we realized the detection of diamino-pentazolium cation (DAPZ+) in the reaction solution experimentally and proved it to be meta-diamino-pentazole based on the transition state theory. Quantum chemical methods were used to predict its spectral properties, charge distribution, stability and aromaticity. Considering that DAPZ+ has excellent detonation properties, it was further explored by assembling it with N5−, N3− and C(NO2)3− anions, respectively. The results show a strong interaction between DAPZ+ and the three anions, which will have a positive effect on its stability. Thanks to the high enthalpy of formation and density, the calculated detonation properties of the three systems are exciting, especially [DAPZ+][N5−] (D: 10,016 m·s−1; P: 37.94 GPa), whose actual detonation velocity may very likely exceed CL-20 (D: 9773 m·s−1). There is no doubt that this work will become the precursor for the theoretical exploration of new polynitrogen ionic compounds.

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Why does the cyclic pentazolate anion fail to undergo N-oxidization in oxone solution?

Abstract: When cyclo-pentazolate anion (N5-) was treated with Oxone, a peak of m/z = 86 in the Liquid Chromatograph Mass Spectrometer (LC-MS) was detected, the same molecular weight as the pentazolate...

Cited by 3 publications

References 29 publications

A molecular dynamics simulation study of thermal transport in hydrazinium cyclo-pentazolate

A molecular dynamics simulation study of thermal transport in hydrazinium cyclo-pentazolate

Insight into the Stability of Pentazolyl Derivatives based on Covalent Bond

Experimental detection of the diamino-pentazolium cation and theoretical exploration of derived high energy materials

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