Chiral polytungstometalates [WM3(H2O)2(XW9O34)2]12–(X = M = Zn or CoII) and their M-substituted derivatives. Syntheses, chemical, structural and spectroscopic study of some<scp>D</scp>,<scp>L</scp>sodium and potassium salts

Tourné, Claude M.; Tourné, Gilbert F.; Zonnevijlle, F.

doi:10.1039/dt9910000143

Cited by 171 publications

(105 citation statements)

References 37 publications

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“…Such a strategy was very successful and reliable in the past for the synthesis of transition metal substituted ªsandwichº compounds. [21] In this case, yields for the metathetical exchange reaction were in the range of 50 ± 65 %.…”

Section: Resultsmentioning

confidence: 84%

The Nickel-Substituted Quasi-Wells-Dawson-Type Polyfluoroxometalate, [NiII(H2O)H2F6NaW17O55]9−, as a Uniquely Active Nickel-Based Catalyst for the Activation of Hydrogen Peroxide and the Epoxidation of Alkenes and Alkenols

2000

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A series of transition metal substituted polyfluorooxometalates (PFOM) [M(L)H2F6NaW17)55]q-, M= Zn2+ , Co2+, Mn2+, Fc2+, 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)H2F6NaW17O55]9- compound was stable under reaction conditions.

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Section: Resultsmentioning

confidence: 84%

The Nickel-Substituted Quasi-Wells-Dawson-Type Polyfluoroxometalate, [NiII(H2O)H2F6NaW17O55]9−, as a Uniquely Active Nickel-Based Catalyst for the Activation of Hydrogen Peroxide and the Epoxidation of Alkenes and Alkenols

2000

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“…The 183 W NMR spectrum has been previously discussed in detail and is indicative of 10 unique W absorptions with one peak for a tungsten atom in the ™belt∫ of the polyoxometalate and nine additional peaks for the tungsten atoms of the ZnW 9 O 34 fragments. [16] 2 ] polyoxometalate is retained upon addition of the hydrogen peroxide. The appearance of two additional distinct peaks at ca.…”

Section: Resultsmentioning

confidence: 99%

“…As is known from the literature, the zinc atoms in the terminal positions, Zn(t) in Scheme 1, can be metathetically exchanged with other transition metals. [16] The transition metal substitution may have a significant effect on the rate of dismutation of hydrogen peroxide and thus on the yield of aqueous biphasic oxidation of organic substrates. We, thus, examined the decomposition of H 2 O 2 in the presence of various transition metal substituted polyoxometalates, Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…[16] Reactions were carried out in 10-mL flasks using the amounts of compounds and conditions as described in the sections above. For example, in the oxidation of alcohols and diols, the substrate (1 mmol) was placed in the reaction flask and 0.6 mL of water was added followed by the addition of 0.1 mL of a 40 mM stock solution of Na q [WZnZn 2 (H 2 O) 2 (Zn-9 O 34 ) 2 ] ¥ x H 2 O and 0.3 mL of 60% aqueous H 2 O 2 .…”

Section: Methodsmentioning

confidence: 99%

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Aqueous Biphasic Oxidation: A Water‐Soluble Polyoxometalate Catalyst for Selective Oxidation of Various Functional Groups with Hydrogen Peroxide

et al. 2004

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and showed only minimal non-productive decomposition of the oxidant. Secondary alcohols were selectively oxidized to ketones, while primary alcohols tended to be oxidized to the corresponding carboxylic acids, although secondary alcohols were selectively oxidized in the presence of primary alcohols. Vicinal diols yielded carbon-carbon bond cleavage products in very high yields. Pyridine derivatives were oxidized to the respective N-oxides, but strongly electron-withdrawing moieties inhibited the oxidation reaction. Primary amines were oxidized to the oximes, but significantly hydrolyzed in situ. Aniline derivatives were oxidized to the corresponding azoxy or nitro products depending on the substitution pattern in the aromatic ring. Catalyst recovery and recycle was demonstrated.

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“…Platinum-containing S-structure polyanions are represented by the not yet fully characterized, [ZnWPt 12À [103] complexes mentioned above. The catalytic activity of such species in the oxidation of different organic substrates has been reported.…”

Section: Platinummentioning

confidence: 99%

Noble Metals in Polyoxometalates

2012

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Polyoxometalates containing noble metal ions, such as ruthenium, osmium, rhodium, palladium, platinum, silver and gold, are a structurally diverse class of compounds. They include both classical heteropolyanions (vanadates, molybdates, tungstates) in which noble metals are present as heteroatoms, as well as the recently discovered class of polyoxometalates with noble metal "addenda" atoms. The focus of this Review is on complexes that should, in principle, exist as discrete molecular species in solution, and which are therefore of interest for their reactivity, their future synthetic utility and potential applications, for example, in catalysis or nanoscience.

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Chiral polytungstometalates [WM₃(H₂O)₂(XW₉O₃₄)₂]^12–(X = M = Zn or Co^II) and their M-substituted derivatives. Syntheses, chemical, structural and spectroscopic study of someD,Lsodium and potassium salts

Cited by 171 publications

References 37 publications

The Nickel-Substituted Quasi-Wells-Dawson-Type Polyfluoroxometalate, [NiII(H2O)H2F6NaW17O55]9−, as a Uniquely Active Nickel-Based Catalyst for the Activation of Hydrogen Peroxide and the Epoxidation of Alkenes and Alkenols

The Nickel-Substituted Quasi-Wells-Dawson-Type Polyfluoroxometalate, [NiII(H2O)H2F6NaW17O55]9−, as a Uniquely Active Nickel-Based Catalyst for the Activation of Hydrogen Peroxide and the Epoxidation of Alkenes and Alkenols

Aqueous Biphasic Oxidation: A Water‐Soluble Polyoxometalate Catalyst for Selective Oxidation of Various Functional Groups with Hydrogen Peroxide

Noble Metals in Polyoxometalates

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Chiral polytungstometalates [WM3(H2O)2(XW9O34)2]12–(X = M = Zn or CoII) and their M-substituted derivatives. Syntheses, chemical, structural and spectroscopic study of someD,Lsodium and potassium salts

Cited by 171 publications

References 37 publications

The Nickel-Substituted Quasi-Wells-Dawson-Type Polyfluoroxometalate, [NiII(H2O)H2F6NaW17O55]9−, as a Uniquely Active Nickel-Based Catalyst for the Activation of Hydrogen Peroxide and the Epoxidation of Alkenes and Alkenols

The Nickel-Substituted Quasi-Wells-Dawson-Type Polyfluoroxometalate, [NiII(H2O)H2F6NaW17O55]9−, as a Uniquely Active Nickel-Based Catalyst for the Activation of Hydrogen Peroxide and the Epoxidation of Alkenes and Alkenols

Aqueous Biphasic Oxidation: A Water‐Soluble Polyoxometalate Catalyst for Selective Oxidation of Various Functional Groups with Hydrogen Peroxide

Noble Metals in Polyoxometalates

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Product

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About

Chiral polytungstometalates [WM₃(H₂O)₂(XW₉O₃₄)₂]^12–(X = M = Zn or Co^II) and their M-substituted derivatives. Syntheses, chemical, structural and spectroscopic study of someD,Lsodium and potassium salts