Protonation of Nitramines: Where does the Proton go
Artikel i vetenskaplig tidskrift, 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

nitramines

protonation

hydrogen fluoride

superacids

Författare

Thomas Saal

Martin Rahm

Chalmers, Kemi och kemiteknik, Kemi och biokemi, Fysikalisk kemi

Karl O. Christe

Ralf Haiges

Angewandte Chemie

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

Vol. 56 32 9587-9591

Ämneskategorier

Oorganisk kemi

DOI

10.1002/ange.201705397