Studies of metallocorroles in low formal oxidation states are quite rare. To address this deficiency, we have examined the stepwise reduction of iron complexes containing the triphenylcorrolate ligand (TPC). Reaction of [FeIII(TPC)(THF)] with KC8 generates the iron corrole anion, [FeII(TPC)]−. Isolation and crystallographic characterization of K(THF)2[FeII(TPC)] represents the first instance of a fully characterized corrole complex of divalent iron. This novel metallocorrole system has shown reactivity towards iodoalkanes generating relatively stable iron(IV) alkyl complexes. Additionally, catalytic reactions with K(THF)2[FeII(TPC)] and terminal alkyl azides results two different reaction pathways. In the presence of di-tert-butyl dicarbonate (Boc2O), the reaction results in a Boc protected terminal amine or in the case of (4-azidobutyl)benzene the Boc protected 2-phenylpyrrolidine. However, in the absence of Boc2O, terminal azides are converted to terminal nitriles. The chemistry of these complexes is discussed and compared with that of more well-known iron porphyrinates.

Reactivity of low-valent iron corroles

ACS Spring Meeting 2021

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