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The synthesis of the first example of a third-row metallocorrolazine characterized by single crystal X-ray diffraction is reported. This Re(V)(O) porphyrinoid complex shows an exclusively ligand-based reactivity with strong acids and oxidizing agents. The one-electron oxidized π-radical-cation complex is capable of H-atom abstraction.

Rhenium(v)–oxo corrolazines: isolating redox-active ligand reactivity