High-valent cobalt–oxo complexes are reactive transient intermediates in a number of oxidative transformation processes e.g., water oxidation and oxygen atom transfer reactions. Studies of cobalt–oxo complexes are very important for understanding the mechanism of the oxygen evolution center in natural photosynthesis, and helpful to replicate enzyme catalysis in artificial systems. This review summarizes the development of identification of high-valent cobalt–oxo species of tetrapyrrolic macrocycles and N-based ligands in oxidation of organic substrates, water oxidation reaction and in the preparation of cobalt–oxo complexes.

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Four cobalt corrole complexes bearing 0–3 cyano groups on the para-position of the three meso-phenyl rings of the macrocycle were synthesized, characterized and applied for electrocatalytic H2 production in both organic solvent and neutral aqueous media.