Johannes E. M. N. Klein

Isoporphyrins have recently been identified as remarkable species capable of turning the nucleophile attached to the porphyrin ring into an electrophile, thereby providing umpolung of reactivity ( Inorg. Chem . 2022 , 61 , 8105–8111). They are generated by nucleophilic attack on an iron(III) π‐dication, a class of species that has received scant attention. Here, we explore the effect of the porphyrin meso ‐substituent and report a iron(III) π‐dication bearing the meso ‐tetraphenylporphyrin (TPP) ligand. We provide an extensive study of the species by UV/Vis absorption, 2 H NMR, EPR, applied field Mössbauer, and resonance Raman spectroscopy. We further explore the system's highly dynamic and tunable properties and address the nature of the axial ligands as well as the conformation of the porphyrin ring. The insights presented are essential for the rational design of catalysts for the umpolung of nucleophiles. Such catalytic avenues could for example provide a novel method for electrophilic chlorinations. We further examine the importance of electronic tuning of the porphyrin by nature of the meso ‐substituent as a factor in catalyst design.