Protonation of Nitramines: Where does the Proton go
Journal article, 2017

The reactions of nitramine, N-methyl nitramine and N,N-dimethyl nitramine with anhydrous HF and the superacids HF/MF5 (M = As, Sb) were investigated at temperatures below -40 °C. In solution, exclusive O-protonation was observed by multinuclear NMR spectroscopy. Whereas no solid product could be isolated from the neat HF solutions even at -78 °C, in the HF/MF5 systems, protonated nitramine MF6- salts were isolated for the first time as moisture-sensitive solids that decompose at temperatures above -40 °C. In the solid state, depending on the counter-ion, O-protonated or N-protonated cations can be formed, in accord with theoretical calculations which show that the energy differences between O-protonation and N-protonation are very small. The [H2N-NO2H][AsF6], [H3N-NO2][SbF6], [MeHNNO2H][SbF6], and [Me2NNO2H][SbF6] salts were characterized by their X-ray crystal structures.

nitrate ions



hydrogen fluoride



Thomas Saal

Martin Rahm

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry, Physical Chemistry

Karl O. Christe

Ralf Haiges

Angewandte Chemie

0044-8249 (ISSN) 1521-3757 (eISSN)

Vol. 56 32 9587-9591

Subject Categories

Inorganic Chemistry



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