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Catalytic peroxide oxidation: The structure of key intermediates in the VV/H2O2 system according to quantum chemical data

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Abstract

The inner-sphere isomerization of the peroxo complexes of vanadium(V) with the general formula [VO6]− was studied using approximations based on the density functional theory (B3LYP/6-31G**) and the Møller-Plesset perturbation theory (MP2/6-31G**). It was found that the complex [V(=O)(ηO2)(O3)]− containing the O3 group as a bidentate ligand was the most stable isomer. The transition state region of a rear-rangement of the triperoxo complex [V(ηO2)3]− into [V(=O)(ηO2)(O3)]− was localized. It was found that the activation barrier (∼30 kcal/mol) was mainly due to O-O bond cleavage in the peroxo ligand. According to calculations, the reaction proceeds through two intermediate complexes whose structure can be interpreted as that containing coordinated singlet dioxygen (especially in the limiting case) because of noticeably shortened O-O bonds in the ηO2 ligand. The calculated reaction scheme of the conversion of [V(ηO2)3]− into [V(=O)(ηO2)(O3)]− is qualitatively consistent with the previously found kinetics of the formation of ozone and the oxidation of alkanes, olefins, arenes, and singlet dioxygen traps.

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Authors and Affiliations

  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991, Russia

    A. A. Markov, S. P. Dolin, N. I. Moiseeva, A. E. Gekhman & I. I. Moiseev

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  1. A. A. Markov
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  2. S. P. Dolin
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  3. N. I. Moiseeva
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  4. A. E. Gekhman
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  5. I. I. Moiseev
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Correspondence to A. A. Markov.

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Original Russian Text © A.A. Markov, S.P. Dolin, N.I. Moiseeva, A.E. Gekhman, I.I. Moiseev, 2009, published in Kinetika i Kataliz, 2009, Vol. 50, No. 5, pp. 683–692.

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Markov, A.A., Dolin, S.P., Moiseeva, N.I. et al. Catalytic peroxide oxidation: The structure of key intermediates in the VV/H2O2 system according to quantum chemical data. Kinet Catal 50, 656–665 (2009). https://doi.org/10.1134/S0023158409050061

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