Mechanism of thermolysis of hydroxylamino-dinitroethylenes

Promising energetic materials—1,1-diamino-2,2-dinitroethylene (DADNE) derivatives in which one or both hydrogen atoms of the amino group are substituted by the OH group were studied by quantum chemical methods using PBE0 hybrid functional with the cc-pVDZ basis set and the coupled cluster method on...

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Bibliographic Details
Published in:Theoretical chemistry accounts 2021-11, Vol.140 (11), Article 149
Main Authors: Krisyuk, B. E., Sypko, T. M.
Format: Article
Language:English
Subjects:
Atomic/Molecular Structure and Spectra
Chemistry
Chemistry and Materials Science
Energetic materials
Enthalpy
Hydrogen atoms
Hydroxyl groups
Inorganic Chemistry
Organic Chemistry
Physical Chemistry
Quantum chemistry
Regular Article
Theoretical and Computational Chemistry
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Summary:Promising energetic materials—1,1-diamino-2,2-dinitroethylene (DADNE) derivatives in which one or both hydrogen atoms of the amino group are substituted by the OH group were studied by quantum chemical methods using PBE0 hybrid functional with the cc-pVDZ basis set and the coupled cluster method on the CCSD/aug-cc-pVDZ level. A series of primary steps of thermolysis were studied, and it has been shown that introduction of the hydroxyl group leads to a change in the mechanism of the rate-determining step. In contrast to the DADNE, for hydroxyl derivatives a number of additional reactions involving the hydroxyl group are possible and the rate-determining stage of thermolysis is the reaction of transfer of the H atom from -OH group to a carbon atom. At the same time, the activation enthalpy decreases sharply from 200 for DADNE to 110 kJ mol –1 for mono- and 90 kJ mol –1 for disubstituted DADNE.
ISSN:1432-881X
1432-2234
DOI:10.1007/s00214-021-02851-9