Abstract: | First evidence for the existence of free trifluoromethyl anion CF3? has been obtained. The 3D‐caged potassium cation in [K(crypt‐222)]+ is inaccessible to CF3?, thus rendering it uncoordinated (“naked”). Ionic [K(crypt‐222)]+ CF3? has been characterized by single‐crystal X‐ray diffraction, solution NMR spectroscopy, DFT calculations, and reactivity toward electrophiles. |