Crystalline, Lewis Base-Free, Cationic Phosphoranimines (Iminophosphonium Salts)

Cationic phosphoranimines have been postulated as intermediates in phosphazene polymerization chemistry. However, the high electrophilicity of the phosphorus center has so far prevented their characterization. Here, we report the synthesis of two Lewis base-free iminophosphonium salts, obtained by reaction of a stable phosphinonitrene with methyl trifluoromethanesulfonate and trifluoromethanesulfonic acid. These cationic species were characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Using 4-(dimethylamino)pyridine, a corresponding Lewis-base adduct has also been isolated.