Computational Study of Main Mechanisms for Gas-Phase Decomposition of 1,1- and 1,2-Dinitroethane

Tsyshevsky, Roman; Аристов, И. В.; Чачков, Д. В.; Шамов, А. Г.; Храпковский, Г. М.

doi:10.1080/07370651003800932

Cited by 4 publications

(5 citation statements)

References 17 publications

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“…The C–NO 2 bond dissociation energy was found to be 72.0 kcal/mol in good agreement with previous computational estimations (70 kcal/mol at the B3P86 level and ∼73 kcal/mol according to G2-based estimations) . Note that D 0 (C–NO 2 ) in dinitroalkanes is profoundly lower (e.g., ∼49 kcal/mol in dinitromethane and gem -dinitroethane). , The higher stability of 1 might be attributed to conjugation between the π orbital of a double CC bond and lone pairs of nitrogen atoms from NO 2 groups.…”

Section: Results and Discussionsupporting

confidence: 88%

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Unexpected Primary Reactions for Thermolysis of 1,1-Diamino-2,2-dinitroethylene (FOX-7) Revealed by ab Initio Calculations

Kiselev

Gritsan

2014

J. Phys. Chem. A

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The primary thermolysis reactions of a promising insensitive explosive 1,1-diamino-2,2-dinitroethylene (DADNE, FOX-7) have been studied in the gas phase at a high level of theory (CCSD(T)-F12/aVTZ). Our calculations revealed that none of the conventional reactions (C-NO2 bond fission, nitro-nitrite and nitro-aci-nitro rearrangements) dominate thermolysis of FOX-7. On the contrary, two new decomposition pathways specific for this particular species that commenced with enamino-imino isomerization and intramolecular cyclization were found instead to be more feasible energetically. The activation barriers of these primary isomerization reactions were calculated to be 48.4 and 28.8 kcal/mol, while the activation energies of the overall decomposition pathways are predicted to be ∼49 and ∼56 kcal/mol, respectively. The new pathways can also be relevant for a wide series of unsaturated hydrocarbons substituted with both nitro- and amino-groups (e.g., triaminotrinitrobenzene, TATB).

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Section: Results and Discussionsupporting

confidence: 88%

“…25 Note that D 0 (C−NO 2 ) in dinitroalkanes is profoundly lower (e.g., ∼49 kcal/mol in dinitromethane and gem-dinitroethane). 49,51 The higher stability of 1 might be attributed to conjugation between the π orbital of a double CC bond and lone pairs of nitrogen atoms from NO 2 groups.…”

Section: ■ Computational Methodsmentioning

confidence: 99%

Unexpected Primary Reactions for Thermolysis of 1,1-Diamino-2,2-dinitroethylene (FOX-7) Revealed by ab Initio Calculations

Kiselev

Gritsan

2014

J. Phys. Chem. A

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“…Indeed, a difference lower than 2 kcal mol À1 in the activation energies between the two reactions was calculated (considering DE or DH), as can be seen in Table 3, according to the results obtained from previous studies on nitroalkanes. 22,24 The next step of the study concerned the influence of structural molecular features on the competition between the two main mechanisms highlighted for 1,1,1-trinitrobutane, i.e. the breaking of the C-NO 2 bond and the HONO elimination.…”

Section: Decomposition Of 111-trinitrobutanementioning

confidence: 99%

“…The thermal decomposition of nitro compounds has been studied in numerous experimental [18][19][20][21] and computational studies. 16,17,[22][23][24][25][26] Different decomposition paths depending upon the type of nitro compounds under investigation 27 were thus suggested, and in particular for nitroalkanes. 28 The main reactions extracted from the literature focused on the decomposition of nitroalkanes are presented in Fig.…”

Section: Introductionmentioning

confidence: 99%

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Decomposition mechanisms of trinitroalkyl compounds: a theoretical study from aliphatic to aromatic nitro compounds

Fayet

Rotureau

Minisini

2014

Phys. Chem. Chem. Phys.

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The chemical mechanisms involved in the decomposition of trinitroethyl compounds were studied for both aliphatic and aromatic derivatives using density functional theory calculations. At first, in the case of 1,1,1-trinitrobutane, used as a reference molecule, two primary channels were highlighted among the five investigated ones: the breaking of the C-N bond and the HONO elimination. Then, the influence of various structural parameters was studied for these two reactions by changing the length of the carbon chain, adding substituents or double bonds along the carbon chain. If some slight changes in activation energies were observed for most of these features, no modification of the competition between the two investigated reactions was highlighted and the breaking of the C-N bond remained the favoured mechanism. At last, the reactions involving the trinitroalkyl fragments were highlighted to be more competitive than reactions involving nitro groups linked to aromatic cycles in two aromatic systems (4-(1,1,1-trinitrobutyl)-nitrobenzene and 2-(1,1,1-trinitrobutyl)-nitrobenzene). This showed that aromatic nitro compounds with trinitroalkyl derivatives decompose from their alkyl part and may be considered more likely as aliphatic than as aromatic regarding the initiation of their decomposition process.

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Estimations of activation and enthalpies of reaction for HONO elimination from C2–C4 mononitroalkanes: A theoretical study

Храпковский

Шамов

Tsyshevsky

et al. 2011

Computational and Theoretical Chemistry

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Computational Study of Main Mechanisms for Gas-Phase Decomposition of 1,1- and 1,2-Dinitroethane

Cited by 4 publications

References 17 publications

Unexpected Primary Reactions for Thermolysis of 1,1-Diamino-2,2-dinitroethylene (FOX-7) Revealed by ab Initio Calculations

Unexpected Primary Reactions for Thermolysis of 1,1-Diamino-2,2-dinitroethylene (FOX-7) Revealed by ab Initio Calculations

Decomposition mechanisms of trinitroalkyl compounds: a theoretical study from aliphatic to aromatic nitro compounds

Estimations of activation and enthalpies of reaction for HONO elimination from C2–C4 mononitroalkanes: A theoretical study

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