Selective Oxidation of Alkylarenes with H2O2 Catalyzed by γ-Keggin Divanadium-substituted Polyoxometalate | Sciact - CRIS-system of Boreskov Institute of Catalysis

Selective Oxidation of Alkylarenes with H2O2 Catalyzed by γ-Keggin Divanadium-substituted Polyoxometalate Conference Abstracts

Conference

EuropaCat-XII: 12th European Congress on Catalysis “Catalysis: Balancing the use of fossil and renewable resources”
30 Aug - 4 Sep 2015 , Казань

Source

EuropaCat XII. Catalysis: Balancing the use of fossil and renewable resources. XII European Congress on Catalysis, Kazan (Russia), 30 August - 4 September, 2015 : Book of Abstracts
Compilation, BIC SB RAS. Novosibirsk.2015. 2184 c. ISBN 978-5-906376-10-7. РИНЦ

Output data

Year: 2015, Article number : IV-PP125, Pages count : 2

Authors

Skobelev I.Y. ¹ , Zalomaeva O.V. ¹ , Evtushok V.Yu. ^1,2 , Maksimov G.M. ¹ , Kholdeeva O.A. ^1,2 , Carbo J.J. ³ , Poblet J.M. ³

Affiliations

1	Boreskov Institute of Catalysis, Novosibirsk, Russia
2	Novosibirsk State University, Novosibirsk, Russia
3	Universitat Rovira i Vigili Marcel lí Domingo, Tarragona, Spain

Funding (4)

1	Russian Foundation for Basic Research	13-03-12042
2	Russian Foundation for Basic Research	14-03-31431
3	Rovira i Virgili University
4	European Cooperation in Science and Technology

The possibility of application of [γ-PW10V2O40] 5- polyoxometalate as catalyst for the selective oxidation of pseudocumene (PC) and 2-methylnaphthalene (2-MN) with H2O2 in MeCN/tBuOH solvent (1:1 v/v) in the presence of mineral acid was explored .The reaction mechanism was studied by experimental and theoretical methods. Unusually high chemo- and regioselectivity towards 2,3,5-trimethylphenol (TMP) was found in PC oxidation. Atypical regioselectivity was found in the oxidation of 2-MN where 6-methyl-1,4-naphthoquinone predominates over 2-methyl-1,4-naphthoquinone. DFT studies revealed that the formation of 2,3,5-TMP in PC oxidation is, most likely, due to peroxo complex [γ-PW10O38V2(O2)]3- (I), which may arise from dehydration of hydroperoxo complex [γ-PW10O38V2(OH)(OOH)]3- formed upon interaction of the H2[γ-PW10V2O40] 3- with Н2О2. The kinetic regularities and estimated rate constants acquired from the kinetic study on PC oxidation with H2O2 are in good agreement with the theoretically predicted reaction mechanism where I is the main active species responsible for the aromatic ring hydroxylation.

Skobelev I.Y. , Zalomaeva O.V. , Evtushok V.Y. , Maksimov G.M. , Kholdeeva O.A. , Carbo J.J. , Poblet J.M.
Selective Oxidation of Alkylarenes with H2O2 Catalyzed by γ-Keggin Divanadium-substituted Polyoxometalate
In compilation EuropaCat XII. Catalysis: Balancing the use of fossil and renewable resources. XII European Congress on Catalysis, Kazan (Russia), 30 August - 4 September, 2015 : Book of Abstracts. – BIC SB RAS., 2015. – C.1595-1596. – ISBN 978-5-906376-10-7.

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