Oxoferryl π‐Cation Radical of β‐Pyrrole Octachlorinated meso‐Tetramesitylporphyrin: Electronic and Structural Properties

Despite significantly different molecular structures and redox potentials, the electronic properties of the oxoferryl cation radical of 1 (M  Fe^IV O instead of M  Fe^IIICl, obtained by oxidation of 1 with m‐chloroperoxyben zoic acid), which shows saddle‐shaped distortions as a result of its peripheral chloro substituents, are similar to those of the corresponding cation radical of the unsubstituted “planar” porphyrin. These results help in the understanding of the different chemoand regioselectivities of halogenated and halogen‐free iron porphyries in the catalytic hydroxylation of alkanes. R  2,4,6 Me₃C₆H₂.