Mixed Valence (μ‐Phenoxido) Fe^IIFe^III and Fe^IIIFe^IV Compounds: Electron and Proton Transfers

Abstract

Mixed‐valence non‐heme diiron centers are present at the active sites of a few enzymes and confer them interesting reactivities with the two ions acting in concert. Related (μ‐phenoxido)diiron complexes have been developed as enzyme mimics. They exhibit very rich spectroscopic properties enabling independent monitoring of each individual ion, which proved useful for mechanistic studies of catalytic hydrolysis and oxidation reactions. In our studies of such complexes, we observed that these compounds give rise to a wide variety of electron transfers (intervalence charge transfer), proton transfers (tautomerism), coupled electron and proton transfers (H. abstraction and PCET). In this minireview, we present and analyze the main results illustrating the latter aspects.