Multielectron Redox Chemistry of Iron Porphyrinogens

Iron octamethylporphyrinogens were prepared and structurally characterized in three different oxidation states in the absence of axial ligands and with sodium or tetrafluoroborate as the only counterions. Under these conditions, the iron- and ligand-based redox chemistry of iron porphyrinogens can be defined. The iron center is easily oxidized by a single electron (E_1/2 = −0.57 V vs NHE in CH₃CN) when confined within the fully reduced macrocycle. The porphyrinogen ligand also undergoes oxidation but in a single four-electron step (E_p = +0.77 V vs NHE in CH₃CN); one of the ligand-based electrons is intercepted for the reduction of Fe(III) to Fe(II) to result in an overall three-electron oxidation process. The oxidation equivalents in the macrocycle are stored in C^α−C^α bonds of spirocyclopropane rings, formed between adjacent pyrroles. EPR, magnetic and Mössbauer measurements, and DFT computations of the redox states of the iron porphyrinogens reveal that the reduced ligand gives rise to iron in intermediate spin states, whereas the fully oxidized ligand possesses a weaker σ-donor framework, giving rise to high-spin iron. Taken together, the results reported herein establish a metal−macrocycle cooperativity that engenders a multielectron chemistry for iron porphyrinogens that is unavailable to heme cofactors.