AgIII compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement of Ag catalysts in cross-coupling via 2e- redox sequences is frequently discarded. Nevertheless, organosilver(III) compounds have been authenticated using tetradentate macrocycles or perfluorinated groups as supporting ligands, and since 2014, first examples of cross-coupling enabled by AgI /AgIII redox cycles saw light. This review collects the most relevant contributions to this field, with main focus on aromatic fluorination/perfluoroalkylation and the identification of AgIII key intermediates. Pertinent comparison between the activity of AgIII RF compounds in aryl-F and aryl-CF3 couplings vs. the one shown by its CuIII RF and AuIII RF congeners is herein disclosed, thus providing a more profound picture on the scope of these transformations and the pathways commonly associated to C-RF bond formations enabled by coinage metals.
Keywords: AgI/AgIII Redox Sequences; AgIII Chemistry; Cross-Coupling; Fluorination; Trifluoromethylation.
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