Oxidations with peroxotungsten complexes: rates and mechanism of stoichiometric olefin epoxidations

Amato, Gaetano; Arcoria, A.; Ballistreri, Francesco P.; Tomaselli, Gaetano A.; Bortolini, Olga; Conte, Valeria; Furia, Fulvio Di; Modena, G.; Valle, Giovanni

doi:10.1016/0304-5102(86)85006-4

Cited by 55 publications

(31 citation statements)

References 5 publications

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“…The small reactivity of monoperoxomolybdenum compounds was supported by experiments [10,43] and a recent theoretical [18] study. However, the data provided in Table 3 reveal that the reactivities of the tungsten compounds are different.…”

Section: (Ii) Reactivity Of Monoperoxo Complexesmentioning

confidence: 75%

Olefin Epoxidation with Transition Metal η2-Peroxo Complexes: The Control of Reactivity

Deubel

Frenking

2001

Eur. J. Inorg. Chem.

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The activation energies for olefin epoxidation with Mimountype η 2 -peroxo complexes have been calculated using density functional methods. Six degrees of freedom of the complex [MOL(O 2 )(OER 3 )] and the olefin CH 2 CHRЈ have been systematically modified. The calculations were based on the assumptions that the reaction follows a concerted oxygentransfer mechanism suggested by Sharpless and that a peroxo oxygen atom trans to the phosphane oxide ligand is transferred. This was recently proved for the epoxidation of ethylene with the parent complex [MoO(O 2 ) 2 {OP(CH 3 ) 3 }]. It has been found that the diperoxotungsten complexes (M = W; L = O 2 ) are more reactive than the diperoxomolybdenum complexes (M = Mo; L = O 2 ). The activation barriers for the monoperoxomolybdenum complexes (M = Mo; L = O) are

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Section: (Ii) Reactivity Of Monoperoxo Complexesmentioning

confidence: 75%

Olefin Epoxidation with Transition Metal η2-Peroxo Complexes: The Control of Reactivity

Deubel

Frenking

2001

Eur. J. Inorg. Chem.

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“…As can be seen, the prepared material shows higher activity in the epoxidation of olefins with inner double bonds which have higher electron density with respect to the terminal ones. It has been have shown that the mechanism of the oxygentransfer to the olefin involves the attack of olefin as nucleophile to the peroxygens of the tungsten-peroxo complex formed in the initial step of the reaction as electrophile [34,35]. Thus, more nucleophilicity of the double bond increases the rate of the epoxidation reaction.…”

Section: Resultsmentioning

confidence: 97%

Wells–Dawson heteropoly acid encapsulated into the nanocages of SBA-16 as heterogeneous catalyst for the oxidation of olefins and alcohols

et al. 2015

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Wells-Dawson type 18-tungstophosphoric acid (H 6 P 2 W 18 O 62 ) as guest was encapsulated inside the nanocages of mesoporous SBA-16 host. The pore entrance of SBA-16 material was modified by silylating reagent to prevent the escape of encapsulated H 6 P 2 W 18 O 62 from the nanocages. The prepared host-guest material was characterized by different physicochemical techniques. X-ray diffraction and transmission electron microscopy analyses indicated the retention of mesoporous structure of SBA-16 and well-dispersion of the H 6 P 2 W 18 O 62 into the nanocages of SBA-16. The obtained material exhibited high catalytic activity, stability, and recyclability in the epoxidation of olefins and oxidation of alcohols in the presence of H 2 O 2 as oxidant.

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“…The alkyl substitution increases electron density of the C=C double bond and raises the π (C=C) HOMO energy, resulting in an increase of the reactivity of the olefin with electrophilic oxidants without steric hindrance such as peroxyacids, peroxides, and peroxo complexes (see Refs [35][36][37][38][39][40][41][42]…”

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confidence: 99%

Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ-SiW10O34(H2O)2]4−

Kamata

Nakagawa

Yamaguchi

et al. 2004

Journal of Catalysis

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Oxidations with peroxotungsten complexes: rates and mechanism of stoichiometric olefin epoxidations

Cited by 55 publications

References 5 publications

Olefin Epoxidation with Transition Metal η2-Peroxo Complexes: The Control of Reactivity

Olefin Epoxidation with Transition Metal η2-Peroxo Complexes: The Control of Reactivity

Wells–Dawson heteropoly acid encapsulated into the nanocages of SBA-16 as heterogeneous catalyst for the oxidation of olefins and alcohols

Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ-SiW10O34(H2O)2]4−

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