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Saddle‐shaped hemes have been discovered in the structures of most peroxidases. How such a macrocycle deformation affects the reaction of FeIII hemes with hydrogen peroxide (H2O2) to form high‐valent Fe‐oxo species remains uncertain. Through examination of the ESI‐MS spectra, absorption changes and 1H NMR chemical shifts, we investigated the reactions of two FeIII porphyrins with different degrees...