Metal- versus ligand-centered reactivity of a cobalt-phenylenediamide complex with electrophiles

A new series of [Co^III-CF₃] complexes supported by a bidentate redox-active ligand is presented. The cationic [Co-CF₃]⁺ complex was first obtained by reacting [CpCo(opda)] (Cp = cyclopentadienyl, opda = o-phenylenediamide) with an electrophilic trifluoromethyl source, for which the redox-active phenylenediamide ligand serves as a 2e^- reservoir to generate [CpCp(bqdi)(CF₃)]⁺ (bqdi = benzoquinonediimine). Electrochemical studies of [Co-CF₃]⁺ revealed two reversible 1e^- reductions. Chemical reduction with 1 or 2 equiv. reducing agent enabled isolation of the neutral and anionic complexes, respectively, where the [Co^III-CF₃] bond remains intact in all three oxidation states (n = +1, 0, -1). Structural analysis shows systematic changes to the redox-active ligand backbone upon reduction, consistent with sequential ligand-centered electron transfer in the series [bqdi]⁰ to [s-bqdi]˙^- to [opda]^2-. In contrast, the reaction of [CpCo(opda)] with alkyl triflates resulted in ligand-centered alkylation at the ureayl groups instead of the targeted Co-alkyl bond formation, suggesting less favorable bond formation at cobalt and greater nucleophilic accessibility of the ligand compared to the metal center.