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

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

Результат исследования: Научные публикации в периодических изданияхстатья

1 Цитирования (Scopus)

Аннотация

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.

Язык оригиналаанглийский
Страницы (с-по)410-416
Число страниц7
ЖурналEuropean Journal of Inorganic Chemistry
Том2019
Номер выпуска3
DOI
СостояниеОпубликовано - 31 янв 2019

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