Microwave‐Assisted Fast Cyclohexane Oxygenation Catalyzed by Iron‐Substituted Polyoxotungstates

Under microwave irradiation, iron‐substituted polyoxotungstates (Fe‐POMs) catalyze cyclohexane oxygenation to A/K oil with 90–95% selectivity, unmatched turnover frequencies (40–400 h−1), and multi‐turnover regime (>1000 TON). Such a rapid reaction protocol allowed the screening of so‐called inorganic Fe‐synzymes with 1–4 nuclearity, including a family of Krebs‐type isostructural complexes. Product distribution, kinetic analysis, mechanistic probes and fitting calculations, are consistent with a radical chain oxidation propagated by Fe‐catalysed decomposition of organic peroxides which ultimately depends on the redox‐properties and structural arrangement of the iron moiety within the POM cage.