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Abstract Visible‐light capture activates a thermodynamically inert CoIII−CF3bond for direct C−H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by a redox‐active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi‐octahedral [(SOCO)CoIII(CF3)(MeCN)2] (
2 ), but in non‐coordinating solvents the complex is red, square pyramidal [(SOCO)CoIII(CF3)(MeCN)] (3 ). Both are thermally stable, and2 is stable in light. But exposure of3 to low‐energy light results in facile homolysis of the CoIII−CF3bond, releasing.CF3radical, which is efficiently trapped by TEMPO.or (hetero)arenes. The homolytic aromatic substitution reactions do not require a sacrificial or substrate‐derived oxidant because the CoIIby‐product of CoIII−CF3homolysis produces H2. The photophysical properties of2 and3 provide a rationale for the disparate light stability.
