High Turnover Numbers for the Catalytic Selective Epoxidation of Alkenes with 1 atm of Molecular Oxygen

Nishiyama, Yoshiyuki; Nakagawa, Yoshinao; Mizuno, Noritaka

doi:10.1002/ange.200790099

Cited by 4 publications

(5 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More recently, we reported the mono- and di-rare-earth-containing 21- and 20-tungstoantimonates(III) [Ln(H 2 O) 4 Sb 2 W 21 O 72 (OH)] 10– (Ln = Yb 3+ , Lu 3+ ) and [Ln 2 (H 2 O) 8 Sb 2 W 20 O 70 ] 8– (Ln = Yb 3+ , Lu 3+ , Y 3+ ), by reaction of [Sb 2 W 22 O 74 (OH) 2 ] 12– with Ln 3+ at different pH . Some other derivatives have also been prepared and their catalytic properties studied, such as water oxidation, epoxidation of alkenes, , Mannich-type reactions, and bioinspired oxygenation …”

Section: Introductionsupporting

confidence: 90%

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage

et al. 2016

View full text Add to dashboard Cite

The gallium(III)-containing heteropolytungstates [Ga4(H2O)10(β-XW9O33)2](6-) (X = As(III), 1; Sb(III), 2) were synthesized in aqueous acidic medium by reaction of Ga(3+) ions with the trilacunary, lone-pair-containing [XW9O33](9-). Polyanions 1 and 2 are isostructural and crystallized as the hydrated sodium salts Na6[Ga4(H2O)10(β-AsW9O33)2]·28H2O (Na-1) and Na6[Ga4(H2O)10(β-SbW9O33)2]·30H2O (Na-2) in the monoclinic space group P21/c, with unit cell parameters a = 16.0218(12) Å, b = 15.2044(10) Å, c = 20.0821(12) Å, and β = 95.82(0)°, as well as a = 16.0912(5) Å, b = 15.2178(5) Å, c = 20.1047(5) Å, and β = 96.2(0)°, respectively. The corresponding tellurium(IV) derivative [Ga4(H2O)10(β-TeW9O33)2](4-) (3) was also prepared, by direct reaction of sodium tungstate, tellurium(IV) oxide, and gallium nitrate. Polyanion 3 crystallized as the mixed rubidium/sodium salt Rb2Na2[Ga4(H2O)10(β-TeW9O33)2]·28H2O (RbNa-3) in the triclinic space group P1̅ with unit cell parameters a = 12.5629(15) Å, b = 13.2208(18) Å, c = 15.474(2) Å, α = 80.52(1)°, β = 84.37(1)°, and γ = 65.83(1)°. All polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR, TGA, and elemental analysis, and polyanion 2 was also characterized in solution by (183)W NMR and UV-vis spectroscopy. Polyanion 2 was used as a homogeneous catalyst toward adenosine triphosphate (ATP) and the DNA model substrate 4-nitrophenylphosphate, monitored by (1)H and (31)P NMR spectroscopy. The encapsulated gallium(III) centers in 2 promote the Lewis acidic synergistic activation of the hydrolysis of ATP and DNA model substrates at a higher rate in near-physiological conditions. A strong interaction of 2 with the P-O bond of ATP was evidenced by changes in chemical shift values and line broadening of the (31)P nucleus in ATP upon addition of the polyanion.

show abstract

Section: Introductionsupporting

confidence: 90%

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage

et al. 2016

View full text Add to dashboard Cite

show abstract

“…In current processes for alkene epoxidation in liquids, an extensive use of expensive oxidants or large doses of co-reagents is usually required 22 – 24 , which inevitably leads to an increase in the costs. To overcome this drawback, several homogeneous catalysts like iron- and ruthenium-substituted polyoxometalates have been developed, allowing O 2 to be the oxidant without a need for any co-reductant 25 , 26 . In contrast, corresponding heterogeneous catalysts are rarely reported.…”

Section: Introductionmentioning

confidence: 99%

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation

et al. 2018

View full text Add to dashboard Cite

Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a “precursor-preselected” wet-chemistry strategy to synthesize highly dispersed Fe2 clusters that are supported on mesoporous carbon nitride (mpg-C3N4). The obtained Fe2/mpg-C3N4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd2 and Ir2, which lays the foundation for discovering diatomic cluster catalysts.

show abstract

“…Keggin and Wells–Dawson structures contain one or more “heteroatoms”, X, in addition to the metal cations and oxide anions and are referred to as “heteropolyanions” (with generic formula of X x M m O v p – ). POMs have a number of attributes that render them attractive for applications in catalysis, materials science, and other technologies. − For example, most POMs are readily prepared in quantity by self-assembly in water from nontoxic and readily available precursors. In addition, almost limitless combinations of elements can be synthetically incorporated into POMs, making it possible to control (fine-tune) virtually all of the molecular properties that impact their potential utility as catalysts, medicines and other functional materials.…”

Section: Introductionmentioning

confidence: 99%

Parameterization of Reactive Force Field: Dynamics of the [Nb₆O₁₉H_x]^(8–x)– Lindqvist Polyoxoanion in Bulk Water

et al. 2013

View full text Add to dashboard Cite

We present results on parameterization of reactive force field [van Duin, A. C. T.; Dasgupta, S.; Lorant, F.; Goddard, W. A. ReaxFF: A Reactive Force Field for Hydrocarbons. J. Phys. Chem. A 2001, 105, 9396-9409] for investigating the properties of the [Nb6O19Hx]((8-x)-) Lindqvist polyoxoanion, x = 0-8, in water. Force-field parameters were fitted to an extensive data set consisting of structures and energetics obtained at the Perdew-Burke-Ernzerhof density functional level of theory. These parameters can reasonably describe pure water structure as well as water with an excess of H(+) and OH(-) ions. Molecular dynamics simulations were performed on [Nb6O19Hx]((8-x)-), x = 0-8, submerged in bulk water at 298 K. Analysis of the MD trajectories showed facile H atom transfer between the protonated polyoxoanion core and bulk water. The number of oxygen sites labeled with an H atom was found to vary depending on the pH of the solution. Detailed analysis shows that the total number of protons at bridging (terminal), η-O (μ2-O), sites ranges from 3(1) at pH 7, to 2(0) at pH 11, to 1(0) at pH 15. These findings closely reflect available experimental measurements.

show abstract

High Turnover Numbers for the Catalytic Selective Epoxidation of Alkenes with 1 atm of Molecular Oxygen

Cited by 4 publications

References 5 publications

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation

Parameterization of Reactive Force Field: Dynamics of the [Nb₆O₁₉H_x]^(8–x)– Lindqvist Polyoxoanion in Bulk Water

Contact Info

Product

Resources

About

High Turnover Numbers for the Catalytic Selective Epoxidation of Alkenes with 1 atm of Molecular Oxygen

Cited by 4 publications

References 5 publications

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage

Gallium(III)-Containing, Sandwich-Type Heteropolytungstates: Synthesis, Solution Characterization, and Hydrolytic Studies toward Phosphoester and Phosphoanhydride Bond Cleavage

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation

Parameterization of Reactive Force Field: Dynamics of the [Nb6O19Hx](8–x)– Lindqvist Polyoxoanion in Bulk Water

Contact Info

Product

Resources

About

Parameterization of Reactive Force Field: Dynamics of the [Nb₆O₁₉H_x]^(8–x)– Lindqvist Polyoxoanion in Bulk Water