Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 5, Pages 1311-1315Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201711693
Keywords
cobalt; ligand effects; photochemistry; reaction mechanisms; trifluoromethylation
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Funding
- National Science Foundation [CHE 1464852]
- Division Of Chemistry [1464852] Funding Source: National Science Foundation
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Visible-light capture activates a thermodynamically inert Co-III-CF3 bond 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 [((OCO)-O-S)Co-III(CF3)(MeCN)(2)] (2), but in non-coordinating solvents the complex is red, square pyramidal [((OCO)-O-S)Co-III(CF3)(MeCN)] (3). Both are thermally stable, and 2 is stable in light. But exposure of 3 to low-energy light results in facile homolysis of the Co-III-CF3 bond, releasing (CF3)-C-. radical, 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 Co-II by-product of Co-III-CF3 homolysis produces H-2. The photophysical properties of 2 and 3 provide a rationale for the disparate light stability.
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