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Issue 4, 2015
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Simple soluble Bi(III) salts as efficient catalysts for the oxidation of alkanes with H2O2

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Abstract

A simple catalytic system based on a soluble bismuth(III) salt, Bi(NO3)3/H2O2/HNO3/CH3CN + H2O, exhibits pronounced activity towards the homogeneous oxidation of inert alkanes with the yield of oxygenate products up to 32% and TON up to 112. The experimental selectivity parameters and kinetic data together with theoretical DFT calculations indicate that the reaction occurs via a free radical mechanism involving the formation of the HO˙ radicals which directly react with alkane molecules. The mechanism of the HO˙ generation (which is the rate limiting step of the whole process) includes the substitution of a water ligand for H2O2 in the initial aqua complex [Bi(H2O)8]3+, hydrolysis of the coordinated H2O2, second H2O-for-H2O2 substitution and the homolytic HO–OH bond cleavage in complex [Bi(H2O)4(H2O2)(OOH)]2+ (6). The relatively low overall activation energy for this process (ca. 20 kcal mol−1) is accounted for by the high lability and acidity of the Bi aqua complexes and tremendous activation of coordinated H2O2 in 6 towards homolysis.

Graphical abstract: Simple soluble Bi(iii) salts as efficient catalysts for the oxidation of alkanes with H2O2

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Publication details

The article was received on 10 Dec 2014, accepted on 12 Jan 2015 and first published on 13 Jan 2015


Article type: Paper
DOI: 10.1039/C4CY01651C
Citation: Catal. Sci. Technol., 2015,5, 2174-2187
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    Simple soluble Bi(III) salts as efficient catalysts for the oxidation of alkanes with H2O2

    B. G. M. Rocha, M. L. Kuznetsov, Y. N. Kozlov, A. J. L. Pombeiro and G. B. Shul'pin, Catal. Sci. Technol., 2015, 5, 2174
    DOI: 10.1039/C4CY01651C

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