Synthesis of Aryl‐Manganese(III) Fluoride Complexes via α‐Fluorine Elimination from CF3 and Difluorocarbene Generation.

We report the synthesis of cyclometalated monoaryl MnIII fluoro complexes using bis(trifluoromethyl)zinc reagent, Zn(CF3)2(DMPU)2, under mild conditions via a reaction pathway that involves initial transmetalation followed by α‐fluorine elimination. The formation of difluorocarbene in these reactions was detected by trapping experiments. Such facile difluorocarbene generation from MnIII results in moderate enhancement of difluoropropanation and difluoropropenation of alkenes and alkynes using Zn(CF3)2(DMPU)2 at lower temperature (20–60 °C) and short reaction time, suggesting potential application of manganese(III) perfluoroalkyl complexes as reactive species for carbene transfer reactivity. [ABSTRACT FROM AUTHOR]