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 inor...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2005-12, Vol.347 (15), p.1909-1912
Main Authors: Bonchio, Marcella, Carraro, Mauro, Scorrano, Gianfranco, Kortz, Ulrich
Format: Article
Language:English
Subjects:
Aerobic oxidation
CH bond activation
homogeneous catalysis
iron
microwave irradiation
polyoxometalates
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Summary: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.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.200505111