Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates: Mechanistic Insights

Olga V. Zalomaeva, Nataliya V. Maksimchuk, Gennadii M. Maksimov, Oxana A. Kholdeeva

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)410-416
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Volume2019
Issue number3
DOIs
Publication statusPublished - 31 Jan 2019

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

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