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.

hydrogen fluoride



nitrate ions



Thomas Saal

University of Southern California

Martin Rahm

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Karl O. Christe

University of Southern California

Ralf Haiges

University of Southern California

Angewandte Chemie

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

Vol. 56 32 9587-9591

Subject Categories

Inorganic Chemistry



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