Evidence of Phosphonium-Carbenium Dication Formation in a Superacid: Precursor to Fluorinated Phosphine Oxides

Unambiguously confirmed by low-temperature in situ NMR experiments, X-ray diffraction and vibrational spectroscopy, phosphonium-carbenium superelectrophiles are shown to be generated in strong acidic conditions. Representing crucial intermediates, their exploitation allows for the synthesis of unprecedented fluorinated (cyclic) phosphine oxides.