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Microwave‐Assisted Fast Cyclohexane Oxygenation Catalyzed by Iron‐Substituted Polyoxotungstates
Author(s) -
Bonchio Marcella,
Carraro Mauro,
Scorrano Gianfranco,
Kortz Ulrich
Publication year - 2005
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200505111
Subject(s) - chemistry , isostructural , cyclohexane , moiety , catalysis , decomposition , redox , selectivity , turnover number , photochemistry , medicinal chemistry , inorganic chemistry , stereochemistry , crystallography , organic chemistry , crystal structure
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.