Generation, Characterization and Reactivity of a High-Valent Mononuclear Cobalt(IV)−Diazide Complex

High-valent Fe(IV)=O intermediates of metalloenzymes have inspired numerous efforts to generate synthetic analogs to mimic and understand their substrate oxidation reactivities. However, high-valent M(IV) complexes of late transition metals are rare. We have recently reported a novel Co(IV)−dinitrate complex (1-NO₃) that activates sp³ C−H bonds up to 87 kcal/mol. In this work, we have shown that the nitrate ligands in 1-NO₃ can be replaced by azide, a more basic coordinating base, resulting in the formation of a more potent Co(IV)−diazide species (1-N₃) that reacts with substrates (hydrocarbons and phenols) at faster rate constants and activates stronger C−H bonds than the parent complex 1-NO₃. We have characterized 1-N₃ employing a combination of spectroscopic and computational approaches. Our results clearly show that the coordination of azide leads to the modulation of the Co(IV) electronic structure and the Co(IV/III) redox potential. Together with the higher basicity of azide, these thermodynamic parameters contribute to the higher driving forces of 1-N₃ than 1-NO₃ for C−H bond activation. Our discoveries are thus insightful for designing more reactive bio-inspired high-valent late transition metal complexes for activating inert aliphatic hydrocarbons.