Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates.
basic_science · Level V
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- Record sourced from PubMed, PMID 38096334.
- Also identified by DOI 10.1126/science.adk4919 and PMC identifier 11827047.
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Abstract
Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity of Ag(II) centers in [Ag(bpy)<sub>2</sub>(TFA)][OTf] and Ag(bpy)(TFA)<sub>2</sub> (bpy, 2,2'-bipyridine; OTf, CF<sub>3</sub>SO<sub>3</sub><sup>-</sup>) complexes to activate trifluoroacetate (TFA) by visible light-induced homolysis. The resulting trifluoromethyl radicals may react with a variety of arenes to forge C(sp<sup>2</sup>)-CF<sub>3</sub> bonds. This methodology is general and extends to other perfluoroalkyl carboxylates of higher chain length (R<sub>F</sub>CO<sub>2</sub><sup>-</sup>; R<sub>F</sub>, CF<sub>2</sub>CF<sub>3</sub> or CF<sub>2</sub>CF<sub>2</sub>CF<sub>3</sub>). The photoredox reaction may be rendered electrophotocatalytic by regenerating the Ag(II) complexes electrochemically during irradiation. Electrophotocatalytic perfluoroalkylation of arenes at turnover numbers exceeding 20 was accomplished by photoexciting the Ag(II)-TFA ligand-to-metal charge transfer (LMCT) state, followed by electrochemical reoxidation of the Ag(I) photoproduct back to the Ag(II) photoreactant.