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An iron porphyrin catalyst with four electron donor groups is reported. The porphyrin ligand bears a distal hydrogen bonding pocket which inverts the normal axial ligand binding selectivity exhibited by porphyrins bearing sterically crowded distal structures. This catalyst specifically reduces O2 by four electrons under both fast and slow electron fluxes at pH 7.

Graphical abstract: Selective four electron reduction of O2 by an iron porphyrin electrocatalyst under fast and slow electron fluxes

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