Iron‐Substituted Polyoxotungstates as Inorganic Synzymes: Evidence for a Biomimetic Pathway in the Catalytic Oxygenation of Catechols

Inorganic Synzymes: Convergent structural, spectroscopic, and mechanistic evidence is presented on the bio-inspired catalysis by FeIII-substituted polyoxotungstates [Fe4(H2O)10(β-XW9O33)2]n− (X=AsIII, SbIII, SeIV, TeIV) in promoting the aerobic cleavage of catechols (see figure). These polyanions display two of the four iron sites with three external and substitution-labile coordination positions typical of non-heme dioxygenase enzymes.