Extremely similar electronic structures and FeO bonding characterize FeIVO S=1 heme and non-heme species as a result of a decoupling of the oxoiron unit from the porphyrin (Por) π system in the heme complex (see scheme). However, along the reaction coordinate towards an FeIIIOH product, the Por π system interacts with the iron d orbitals, thus resulting in different reactivities for heme and non-heme complexes.
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Edward I. Solomon (2005) studied this question.