Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Thioether Oxidation with H2O2 Catalyzed by Nb-Substituted Polyoxotungstates : Mechanistic Insights. / Zalomaeva, Olga V.; Maksimchuk, Nataliya V.; Maksimov, Gennadii M. и др.
в: European Journal of Inorganic Chemistry, Том 2019, № 3, 31.01.2019, стр. 410-416.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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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