Metal complex catalyzed oxidations with hydroperoxides: Inner-sphere electron transfer

Моисеева, Н. И.; Гехман, А. Е.; Моисеев, И. И.

doi:10.1016/s1381-1169(96)00417-7

Cited by 27 publications

(20 citation statements)

References 46 publications

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“…Singlet dioxygen is responsible for the oxidation of anthracene and its derivatives to anthraquinones and for the oxidative degradation of olefins to carbonyl compounds [6,7,9,10,[13][14][15][16]. The scope of reaction mentioned above has been rationalized within speculative Scheme 1, which is in a good agreement with data published in [6,7,9,10,[13][14][15][16].…”

Section: Introductionsupporting

confidence: 79%

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Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

Гехман

Stolyarov

Моисеева

et al. 2004

Comptes Rendus. Chimie

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Section: Introductionsupporting

confidence: 79%

“…Vanadium(V) compounds in AcOH have been shown [8][9][10][11][12] to catalyze H 2 O 2 decomposition leading to the formation of singlet dioxygen 3 O 2 (reactions (1,2)) and small amounts of ozone (reaction (3)):…”

Section: Introductionmentioning

confidence: 99%

Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

Гехман

Stolyarov

Моисеева

et al. 2004

Comptes Rendus. Chimie

Self Cite

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“…This may be rationalized as follows: the disproportionation of peroxo intermediates proceeds through polarization of the metal ± peroxo bonds, Mo ± O 2 , and the peroxide bonds, O ± O, in the peroxomolybdate complex, followed by an inner-sphere two-electron rearrangement. [9,39] Acceleration of peroxide decomposition on a solid support has been observed previously; the homolytic O ± O bond cleavage for alkyl(hydro)peroxides is accelerated in the presence of alkaliexchanged zeolite Y. [40] Similarly, the disproportionation of peroxomolybdate complexes is favored in the vicinity of the highly charged LDH support.…”

Section: Discussionsupporting

confidence: 52%

Kinetic and Spectroscopic Study of¹O₂Generation from H₂O₂Catalyzed by LDH–MoO₄²⁻(LDH=Layered Double Hydroxide)

Sels

Vos

Grobet

et al. 2001

Chemistry A European J

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Layered double hydroxides (LDHs), exchanged with molybdate, decompose H2O2 to form one molecule of singlet-state dioxygen (1O2) from two molecules of H2O2. The dependence of the kinetics of H2O2 decomposition on Mo and H2O2 concentrations and on temperature has been related to structural characteristics of the material (X-ray diffraction (XRD), scanning electron microscopy (SEM), IR spectroscopy, N2 adsorption, thermogravimetry) and to molybdate speciation as revealed by in-situ studies in the presence of peroxide (FT Raman, diffuse reflectance UV/visible spectroscopy). The H2O2 decomposition rate is linearly correlated with the amount of LDH-exchanged molybdate, except when a considerable fraction of the molybdate occupies less accessible interlayer positions. A maximum in the H2O2 decomposition rate as the H2O2 concentration is increased is due to the successive formation of mono-, di-, tri-, and tetraperoxomolybdates. This behavior was modeled successfully by using the equilibrium constants for formation of the Mo-peroxo complexes, and the rate constants for decay of the peroxomolybdates with 1O2 liberation. Time-resolved diffuse reflectance and Raman observations of the various MoO4(2-)-peroxide adducts are in line with the proposed kinetic scheme. Of all the Mo-peroxo species on the LDH, the triperoxomolybdate has the highest rate for decay to 1O2. Comparison with the kinetics of dissolved molybdate shows that the monomolecular decay of all peroxomolybdate species proceeds much faster at the LDH surface than in solution. Consequently, maximal rates per Mo atom are at least twice as high for the heterogeneous LDH catalyst as for the homogeneous systems.

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“…9,10-endoPeroxides are well-known intermediates in anthracene interactions with 1 O 2 and metalloperoxo complexes [26,34]. They are similar to 4, but there are no olefinic double bonds in their structures, so 3-type intermediates cannot be formed.…”

Section: Formation Of 14-naphthoquinone In Naphthalene Oxidation Catmentioning

confidence: 99%

Naphthalene Oxidation by Peracetic Acid Catalysed by Mn(III) Porphine-like Complexes: Nature of Intermediates and Pathways of their Formation

Barkanova

Kaliya

1999

J. Porphyrins Phthalocyanines

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Mn ( III ) complexes of meso-tetra(o,o′-dichlorophenyl)porphyrin, tetra-tert-butyl-tetraazaporphine and 3,5-octanitrophthalocyanine are efficient catalysts of naphthalene oxidation by peracetic acid in acetonitrile solution. The pathways of the reaction and the nature of intermediates and final products depend on the catalyst structure. For meso-tetra(o,o′-dichlorophenyl)porphyrin MnCl and tetra-tert-butyl-tetraazaporphine MnCl the single primary oxidation product is 1-naphthol. For 3,5-octanitrophthalocyanine MnCl, two pathways of naphthalene oxidation yielding 1-naphthol (as the primary product) and 1,4-naphthoquinone are proposed. The pathway of 1,4-naphthoquinone formation in the 3,5-octanitrophthalocyanine MnCl -catalysed reaction seems to involve two intermediates, 1,4-endo-peroxy-1,4-dihydro- and 2,3-epoxy-1,4-endo-peroxy-1,2,3,4-tetrahydronaphthalene.

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Metal complex catalyzed oxidations with hydroperoxides: Inner-sphere electron transfer

Cited by 27 publications

References 46 publications

Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

Kinetic and Spectroscopic Study of¹O₂Generation from H₂O₂Catalyzed by LDH–MoO₄²⁻(LDH=Layered Double Hydroxide)

Naphthalene Oxidation by Peracetic Acid Catalysed by Mn(III) Porphine-like Complexes: Nature of Intermediates and Pathways of their Formation

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Metal complex catalyzed oxidations with hydroperoxides: Inner-sphere electron transfer

Cited by 27 publications

References 46 publications

Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

Kinetic and Spectroscopic Study of1O2Generation from H2O2Catalyzed by LDH–MoO42−(LDH=Layered Double Hydroxide)

Naphthalene Oxidation by Peracetic Acid Catalysed by Mn(III) Porphine-like Complexes: Nature of Intermediates and Pathways of their Formation

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Kinetic and Spectroscopic Study of¹O₂Generation from H₂O₂Catalyzed by LDH–MoO₄²⁻(LDH=Layered Double Hydroxide)