Redox-active ligand promoted electrophile addition at cobalt

The reactivity of an electron-rich cobalt complex bearing an o-phenylenediamide ligand with electrophilic CF3+ and F+ sources is reported. These reactions lead to generation of a Co(iii)-CF3 or Co(iii)-F complex, promoted by redox-active ligand-to-substrate two-electron transfer. The rate of trifluoromethyl addition at cobalt correlates with the potential difference between the cobalt complex and the CF3+ source. We present initial demonstrations of radical trifluoromethylation and nucleophilic fluorination of organic substrates, setting the stage for the development of electrocatalytic pathways for these bond-forming reactions. A cobalt-phenylenediamide complex reacts with electrophilic CF3+ and F+ sources, generating new Co(iii)-CF3 or Co(iii)-F species through ligand-to-substrate two-electron transfer.