Thioether Oxidation with H₂O₂ Catalyzed by Nb-Substituted Polyoxotungstates. Mechanistic Insights Full article
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European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682 |
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| Output data | Year: 2019, Volume: 2019, Number: 3-4, Pages: 410-416 Pages count : 7 DOI: 10.1002/ejic.201801108 | ||||
| Tags | sulfoxidation • niobium •polyoxometalate• Lindqvist structure• hydrogen peroxide | ||||
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| Affiliations |
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Funding (2)
| 1 | Federal Agency for Scientific Organizations | 0303-2016-0005 |
| 2 | Russian Foundation for Basic Research | 16-03-00827 |
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 peroxocomplexes (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.
Cite:
Zalomaeva O.V.
, Maksimchuk N.V.
, Maksimov G.M.
, Kholdeeva O.A.
Thioether Oxidation with H₂O₂ Catalyzed by Nb-Substituted Polyoxotungstates. Mechanistic Insights
European Journal of Inorganic Chemistry. 2019. V.2019. N3-4. P.410-416. DOI: 10.1002/ejic.201801108 WOS Scopus РИНЦ OpenAlex ANCAN
Thioether Oxidation with H₂O₂ Catalyzed by Nb-Substituted Polyoxotungstates. Mechanistic Insights
European Journal of Inorganic Chemistry. 2019. V.2019. N3-4. P.410-416. DOI: 10.1002/ejic.201801108 WOS Scopus РИНЦ OpenAlex ANCAN
Dates:
| Submitted: | Sep 14, 2018 |
| Published online: | Nov 12, 2018 |
| Published print: | Jan 31, 2019 |
Identifiers:
| ≡ Web of science: | WOS:000456856100014 |
| ≡ Scopus: | 2-s2.0-85057988744 |
| ≡ Elibrary: | 38654826 |
| ≡ OpenAlex: | W2901137654 |
| ≡ Chemical Abstracts: | 2018:2391711 |
| ≡ Chemical Abstracts (print): | 170:167897 |