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  1. ; ; ; (, Angewandte Chemie International Edition)
    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, and2is stable in light. But exposure of3to 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 of2and3provide a rationale for the disparate light stability. 
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  2. ; ; ; ; ; ; ; ; ; (, Inorganic Chemistry)
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