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Kinetics and mechanism of the oxidation of 2,3,6-trimethylphenol with hydrogen peroxide in the presence of Ti-monosubstituted polyoxometalates

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Abstract

The product composition and reaction kinetics are reported for 2,3,6-trimethylphenol (TMP) oxidation with hydrogen peroxide in acetonitrile catalyzed by a Ti-monosubstituted polyoxometalate (Ti-POM) with a Keggin structure ([Bu4N]4[PTi(OMe)W11O39]) and for the stoichiometric reaction between TMP and the peroxo complex [Bu4N]4[HPTi(O)2W11O39] (I). The main products of the stoichiometric reaction are 2,3,5-trimethyl-1,4-benzoquinone (TMBQ) and 2,2′,3,3′,6,6′-hexamethyl-4,4′-biphenol (BP). The TMBQ yield increases as the TMP/I molar ratio is decreased. The catalytic reaction is first-order with respect to H2O2 and the catalyst and has a variable order (1-0) with respect to TMP. The rate of the reaction increases as the water concentration in the reaction mixture is raised. The stoichiometric reaction is first-order with respect to peroxo complex I and has a variable order (1-0) with respect to TMP. There is no kinetic isotope effect for this reaction (k ArOH/k ArOD = 1). A TMP oxidation mechanism is suggested, which includes the coordination of a TMP molecule and peroxide on a Ti site of the catalyst with the formation of a reactive intermediate. The one-electron oxidation of TMP in this intermediate yields a phenoxyl radical. The subsequent conversions of these ArO° radicals yield the reaction products.

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Correspondence to T. A. Trubitsyna.

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Original Russian Text © T.A. Trubitsyna, O.A. Kholdeeva, 2008, published in Kinetika i Kataliz, 2008, Vol. 49, No. 3, pp. 392–399.

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Trubitsyna, T.A., Kholdeeva, O.A. Kinetics and mechanism of the oxidation of 2,3,6-trimethylphenol with hydrogen peroxide in the presence of Ti-monosubstituted polyoxometalates. Kinet Catal 49, 371–378 (2008). https://doi.org/10.1134/S0023158408030087

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