The nickel-substituted quasi-Wells-Dawson-type polyfluoroxometalate, [NiII(H2O)H2F6NaW17O 55]9-, as a uniquely active nickel-based catalyst for the activation of hydrogen peroxide and the epoxidation of alkenes and alkenols

Revital Ben-Daniel, Alexander M. Khenkin, Ronny Neumann

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Abstract

A series of transition metal substituted polyfluorooxometalates (PFOM) [M(L)H2F6NaW17O55]q-, M = Zn2+, Co2+, Mn2+, Fe2+, Ru2+, Ni2+ and V5+ and L = H2O, O2-, of quasi-Wells -Dawson structure, was synthesized. In the series prepared, only the nickel-substituted polyfluorooxometalate was capable of catalytic activation of hydrogen peroxide in biphasic reaction media, the reaction leading mainly to the selective epoxidation of alkenes and alkenols. The manganese-, cobalt-, ruthenium-, iron-, vanadium-, and zinc-substituted polyfluorooxometalates were catalytically inactive, although, except for the zinc polyfluorooxometalate, very significant catalase activity was observed. Oxidation of thianthrene showed that sulfoxides were oxidized more easily than sulfides. Kinetic profiles of cyclooctene epoxidation showed that the reaction was zero order in both cyclooctene and hydrogen peroxide. Hydrogen peroxide was consumed at a rate 40% higher than the rate of epoxidation of cyclooctene. The reaction appears to proceed through an intermediate peroxo/hydroperoxo species that was observed in the IR spectrum. Atomic absorption, IR and 19F NMR spectroscopy indicated that the [Ni(H2O)-H2F6NaW17O 55]9- compound was stable under reaction conditions.

Original languageEnglish
Pages (from-to)3722-3728
Number of pages7
JournalChemistry - A European Journal
Volume6
Issue number20
Publication statusPublished - Oct 16 2000

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Epoxidation
Alkenes
Nickel
Hydrogen peroxide
Hydrogen Peroxide
Olefins
Chemical activation
Catalysts
Zinc
Sulfoxides
Vanadium
Ruthenium
Sulfides
Manganese
Cobalt
Catalase
Nuclear magnetic resonance spectroscopy
Transition metals
Iron
Oxidation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "The nickel-substituted quasi-Wells-Dawson-type polyfluoroxometalate, [NiII(H2O)H2F6NaW17O 55]9-, as a uniquely active nickel-based catalyst for the activation of hydrogen peroxide and the epoxidation of alkenes and alkenols",
abstract = "A series of transition metal substituted polyfluorooxometalates (PFOM) [M(L)H2F6NaW17O55]q-, M = Zn2+, Co2+, Mn2+, Fe2+, Ru2+, Ni2+ and V5+ and L = H2O, O2-, of quasi-Wells -Dawson structure, was synthesized. In the series prepared, only the nickel-substituted polyfluorooxometalate was capable of catalytic activation of hydrogen peroxide in biphasic reaction media, the reaction leading mainly to the selective epoxidation of alkenes and alkenols. The manganese-, cobalt-, ruthenium-, iron-, vanadium-, and zinc-substituted polyfluorooxometalates were catalytically inactive, although, except for the zinc polyfluorooxometalate, very significant catalase activity was observed. Oxidation of thianthrene showed that sulfoxides were oxidized more easily than sulfides. Kinetic profiles of cyclooctene epoxidation showed that the reaction was zero order in both cyclooctene and hydrogen peroxide. Hydrogen peroxide was consumed at a rate 40{\%} higher than the rate of epoxidation of cyclooctene. The reaction appears to proceed through an intermediate peroxo/hydroperoxo species that was observed in the IR spectrum. Atomic absorption, IR and 19F NMR spectroscopy indicated that the [Ni(H2O)-H2F6NaW17O 55]9- compound was stable under reaction conditions.",
author = "Revital Ben-Daniel and Khenkin, {Alexander M.} and Ronny Neumann",
year = "2000",
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T1 - The nickel-substituted quasi-Wells-Dawson-type polyfluoroxometalate, [NiII(H2O)H2F6NaW17O 55]9-, as a uniquely active nickel-based catalyst for the activation of hydrogen peroxide and the epoxidation of alkenes and alkenols

AU - Ben-Daniel, Revital

AU - Khenkin, Alexander M.

AU - Neumann, Ronny

PY - 2000/10/16

Y1 - 2000/10/16

N2 - A series of transition metal substituted polyfluorooxometalates (PFOM) [M(L)H2F6NaW17O55]q-, M = Zn2+, Co2+, Mn2+, Fe2+, Ru2+, Ni2+ and V5+ and L = H2O, O2-, of quasi-Wells -Dawson structure, was synthesized. In the series prepared, only the nickel-substituted polyfluorooxometalate was capable of catalytic activation of hydrogen peroxide in biphasic reaction media, the reaction leading mainly to the selective epoxidation of alkenes and alkenols. The manganese-, cobalt-, ruthenium-, iron-, vanadium-, and zinc-substituted polyfluorooxometalates were catalytically inactive, although, except for the zinc polyfluorooxometalate, very significant catalase activity was observed. Oxidation of thianthrene showed that sulfoxides were oxidized more easily than sulfides. Kinetic profiles of cyclooctene epoxidation showed that the reaction was zero order in both cyclooctene and hydrogen peroxide. Hydrogen peroxide was consumed at a rate 40% higher than the rate of epoxidation of cyclooctene. The reaction appears to proceed through an intermediate peroxo/hydroperoxo species that was observed in the IR spectrum. Atomic absorption, IR and 19F NMR spectroscopy indicated that the [Ni(H2O)-H2F6NaW17O 55]9- compound was stable under reaction conditions.

AB - A series of transition metal substituted polyfluorooxometalates (PFOM) [M(L)H2F6NaW17O55]q-, M = Zn2+, Co2+, Mn2+, Fe2+, Ru2+, Ni2+ and V5+ and L = H2O, O2-, of quasi-Wells -Dawson structure, was synthesized. In the series prepared, only the nickel-substituted polyfluorooxometalate was capable of catalytic activation of hydrogen peroxide in biphasic reaction media, the reaction leading mainly to the selective epoxidation of alkenes and alkenols. The manganese-, cobalt-, ruthenium-, iron-, vanadium-, and zinc-substituted polyfluorooxometalates were catalytically inactive, although, except for the zinc polyfluorooxometalate, very significant catalase activity was observed. Oxidation of thianthrene showed that sulfoxides were oxidized more easily than sulfides. Kinetic profiles of cyclooctene epoxidation showed that the reaction was zero order in both cyclooctene and hydrogen peroxide. Hydrogen peroxide was consumed at a rate 40% higher than the rate of epoxidation of cyclooctene. The reaction appears to proceed through an intermediate peroxo/hydroperoxo species that was observed in the IR spectrum. Atomic absorption, IR and 19F NMR spectroscopy indicated that the [Ni(H2O)-H2F6NaW17O 55]9- compound was stable under reaction conditions.

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