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Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates : Mechanistic Insights. / Zalomaeva, Olga V.; Maksimchuk, Nataliya V.; Maksimov, Gennadii M. et al.

In: European Journal of Inorganic Chemistry, Vol. 2019, No. 3, 31.01.2019, p. 410-416.

Research output: Contribution to journal › Article › peer-review

Harvard

Zalomaeva, OV, Maksimchuk, NV, Maksimov, GM & Kholdeeva, OA 2019, 'Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates: Mechanistic Insights', European Journal of Inorganic Chemistry, vol. 2019, no. 3, pp. 410-416. https://doi.org/10.1002/ejic.201801108

APA

Zalomaeva, O. V., Maksimchuk, N. V., Maksimov, G. M., & Kholdeeva, O. A. (2019). Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates: Mechanistic Insights. European Journal of Inorganic Chemistry, 2019(3), 410-416. https://doi.org/10.1002/ejic.201801108

Vancouver

Zalomaeva OV, Maksimchuk NV, Maksimov GM, Kholdeeva OA. Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates: Mechanistic Insights. European Journal of Inorganic Chemistry. 2019 Jan 31;2019(3):410-416. doi: 10.1002/ejic.201801108

Author

Zalomaeva, Olga V. ; Maksimchuk, Nataliya V. ; Maksimov, Gennadii M. et al. / Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates : Mechanistic Insights. In: European Journal of Inorganic Chemistry. 2019 ; Vol. 2019, No. 3. pp. 410-416.

BibTeX

@article{ca4e83851aa544608be259725bb7f5e0,
title = "Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates: Mechanistic Insights",
abstract = "Nb-monosubstituted polyoxotungstates of the Lindqvist and Keggin structures, (Bu4N)3[Nb(O)W5O18] (1) and (Bu4N)4[PW11NbO40] (2), respectively, catalyze oxidation of organic sulfides with aqueous H2O2 in acetonitrile. The corresponding peroxo complexes (Bu4N)3[Nb(O2)W5O18] (3) and (Bu4N)4[PW11Nb(O2)O39] (4), formed upon interaction of 1 and 2 with H2O2, are able to oxidize sulfides to sulfoxides and sulfones under stoichiometric conditions. The product analysis of the oxidation of thianthrene 5-oxide, competitive sulfide–sulfoxide oxidation and Hammett plot implicated electrophilic oxidative properties of 4 and a complex oxidative nature of 3. Protonation of peroxo complex 3 leading to the formation of the peroxo species (Bu4N)2[HNb(O2)W5O18] (5) strongly increases its electrophilicity, which has a great impact on its reactivity and sulfoxidation selectivity.",
keywords = "Homogeneous catalysis, Lindqvist structures, Niobium, Polyoxometalates, Sulfoxidation, SILANOL-FUNCTIONALIZED POLYOXOTUNGSTATES, OXYGEN-TRANSFER, ORGANIC SULFIDES, MESOPOROUS NIOBIUM-SILICATES, SELECTIVE EPOXIDATION, THIANTHRENE 5-OXIDE, VERSATILE CATALYSTS, HYDROGEN-PEROXIDE, ALKENE EPOXIDATION, ARYL METHYL SULFOXIDES",
author = "Zalomaeva, {Olga V.} and Maksimchuk, {Nataliya V.} and Maksimov, {Gennadii M.} and Kholdeeva, {Oxana A.}",
year = "2019",
month = jan,
day = "31",
doi = "10.1002/ejic.201801108",
language = "English",
volume = "2019",
pages = "410--416",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "3",

}

RIS

TY - JOUR

T1 - Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates

T2 - Mechanistic Insights

AU - Zalomaeva, Olga V.

AU - Maksimchuk, Nataliya V.

AU - Maksimov, Gennadii M.

AU - Kholdeeva, Oxana A.

PY - 2019/1/31

Y1 - 2019/1/31

N2 - Nb-monosubstituted polyoxotungstates of the Lindqvist and Keggin structures, (Bu4N)3[Nb(O)W5O18] (1) and (Bu4N)4[PW11NbO40] (2), respectively, catalyze oxidation of organic sulfides with aqueous H2O2 in acetonitrile. The corresponding peroxo complexes (Bu4N)3[Nb(O2)W5O18] (3) and (Bu4N)4[PW11Nb(O2)O39] (4), formed upon interaction of 1 and 2 with H2O2, are able to oxidize sulfides to sulfoxides and sulfones under stoichiometric conditions. The product analysis of the oxidation of thianthrene 5-oxide, competitive sulfide–sulfoxide oxidation and Hammett plot implicated electrophilic oxidative properties of 4 and a complex oxidative nature of 3. Protonation of peroxo complex 3 leading to the formation of the peroxo species (Bu4N)2[HNb(O2)W5O18] (5) strongly increases its electrophilicity, which has a great impact on its reactivity and sulfoxidation selectivity.

AB - Nb-monosubstituted polyoxotungstates of the Lindqvist and Keggin structures, (Bu4N)3[Nb(O)W5O18] (1) and (Bu4N)4[PW11NbO40] (2), respectively, catalyze oxidation of organic sulfides with aqueous H2O2 in acetonitrile. The corresponding peroxo complexes (Bu4N)3[Nb(O2)W5O18] (3) and (Bu4N)4[PW11Nb(O2)O39] (4), formed upon interaction of 1 and 2 with H2O2, are able to oxidize sulfides to sulfoxides and sulfones under stoichiometric conditions. The product analysis of the oxidation of thianthrene 5-oxide, competitive sulfide–sulfoxide oxidation and Hammett plot implicated electrophilic oxidative properties of 4 and a complex oxidative nature of 3. Protonation of peroxo complex 3 leading to the formation of the peroxo species (Bu4N)2[HNb(O2)W5O18] (5) strongly increases its electrophilicity, which has a great impact on its reactivity and sulfoxidation selectivity.

KW - Homogeneous catalysis

KW - Lindqvist structures

KW - Niobium

KW - Polyoxometalates

KW - Sulfoxidation

KW - SILANOL-FUNCTIONALIZED POLYOXOTUNGSTATES

KW - OXYGEN-TRANSFER

KW - ORGANIC SULFIDES

KW - MESOPOROUS NIOBIUM-SILICATES

KW - SELECTIVE EPOXIDATION

KW - THIANTHRENE 5-OXIDE

KW - VERSATILE CATALYSTS

KW - HYDROGEN-PEROXIDE

KW - ALKENE EPOXIDATION

KW - ARYL METHYL SULFOXIDES

UR - http://www.scopus.com/inward/record.url?scp=85057988744&partnerID=8YFLogxK

U2 - 10.1002/ejic.201801108

DO - 10.1002/ejic.201801108

M3 - Article

AN - SCOPUS:85057988744

VL - 2019

SP - 410

EP - 416

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 3

ER -

ID: 17830387