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Catalytic activity of iron-substituted polyoxotungstates in the oxidation of aromatic compounds with hydrogen peroxide

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Abstract

The tetrabutylammonium (TBA) salts of Keggin-type polyoxotungstates of the general formula [XW11FeIII(H2O)O39]n−, where X = P, B or Si, were evaluated as catalysts in the oxidation, under mild conditions, of ethylbenzene, cumene, p-cymene and sec-butylbenzene with aqueous H2O2 in CH3CN at 80 °C. The influence of various factors, such as the substrate/catalyst molar ratio, the amount of oxidant added or the reaction time, was investigated in a systematic way. Generally, the system exhibited moderate conversion, with good selectivity towards the corresponding acetophenone and hydroperoxide. In order to understand the reaction pathways, the oxidation of several products and presumed intermediates was also carried out in the presence of TBA4[PW11Fe(H2O)O39]·2H2O. Under the conditions used, the oxidation of styrene and styrene derivatives gave rise mainly to carbon–carbon double-bond cleavage, affording the corresponding products in very high yields (81–87%). Possible reaction pathways are presented.

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Acknowledgments

Thanks are due to the University of Aveiro and FCT (Fundação para a Ciência e a Tecnologia) for funding. A.C.E. and I.C.M.S.S. also thank FCT for their grants.

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Authors and Affiliations

  1. CICECO, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal

    Ana C. Estrada & Ana M. V. Cavaleiro

  2. QOPNA, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal

    Mário M. Q. Simões, Isabel C. M. S. Santos, M. Graça P. M. S. Neves & José A. S. Cavaleiro

Authors
  1. Ana C. Estrada
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  2. Mário M. Q. Simões
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  3. Isabel C. M. S. Santos
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  4. M. Graça P. M. S. Neves
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  5. José A. S. Cavaleiro
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  6. Ana M. V. Cavaleiro
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Corresponding authors

Correspondence to M. Graça P. M. S. Neves or Ana M. V. Cavaleiro.

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Estrada, A.C., Simões, M.M.Q., Santos, I.C.M.S. et al. Catalytic activity of iron-substituted polyoxotungstates in the oxidation of aromatic compounds with hydrogen peroxide. Monatsh Chem 141, 1223–1235 (2010). https://doi.org/10.1007/s00706-010-0370-9

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  • DOI: https://doi.org/10.1007/s00706-010-0370-9

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