Molecular mechanism of thermal decomposition of fluoronitroazoxy compounds: DFT computational study

•DFT study proves that the mechanism of decomposition of fluoronitroazoxy compounds is quite unlike that previously suggested.•The nature of the substituent and medium polarity do not affect the mechanism of decomposition of fluoronitroazoxy compounds.•Substituent and solvent effects determine the kinetics of decomposition of fluoronitroazoxy compounds to some extent.

Based on DFT computation data, a molecular mechanism of the thermal decomposition of fluoronitroazoxy compounds was studied. The processes were confirmed to proceed through five-membered cyclic Cope transition complexes, even though a different mechanism was previously suggested. Furthermore, it was proved that decomposition kinetics may be somewhat controlled by changing medium polarity and the character of the substituent in the fluoronitroazoxy compound.

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