A Porphyrin Iron(III) π‐Dication Species and its Relevance in Catalyst Design for the Umpolung of Nucleophiles

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, 2H 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. A key intermediate in bioinspired umpolung of nucleophiles is an iron(III) π‐dication. We identify that the meso‐substituent of the porphyrin controls its accessibility and report the detailed study of an iron(III) π‐dication with the meso‐tetraphenylporphyrin ligand. We investigate the dynamics of the system and extensively characterize the species, providing crucial information for future catalyst design. Finally, we correlate the meso‐substituent nature to catalytic chlorination reactivity.