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Copper-catalyzed intramolecular dehydrogenative aminooxygenation: Direct access to formyl-substituted aromatic N-heterocycles

A direct synthesis of carbaldehydes through intramolecular dehydrogenative aminooxygenation has been developed. The process uses a catalytic amount of copper(II) in DMF or DMA under oxygen and does not require additional oxidants (see scheme). Mechanistic studies suggest that the carbonyl oxygen atom of the aldehyde is derived from oxygen through a copper-mediated oxygen activation process via a peroxy-copper(III) intermediate. Copyright

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Compositionally tunable Cu2ZnSn(S1-xSe x)4 nanocrystals: Probing the effect of Se-inclusion in mixed chalcogenide thin films

Nanocrystals of multicomponent chalcogenides, such as Cu 2ZnSnS4 (CZTS), are potential building blocks for low-cost thin-film photovoltaics (PVs). CZTS PV devices with modest efficiencies have been realized through postdeposition annealing at high temperatures in Se vapor. However, little is known about the precise role of Se in the CZTS system. We report the direct solution-phase synthesis and characterization of Cu 2ZnSn(S1-xSex)4 nanocrystals (0 ? x ? 1) with the aim of probing the role of Se incorporation into CZTS. Our results indicate that increasing the amount of Se increases the lattice parameters, slightly decreases the band gap, and most importantly increases the electrical conductivity of the nanocrystals without a need for annealing.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Effect of transition metal diketonates on oxidation of sunflower-seed oil

Effect of transition metal (Mn, Fe, Co, Ni, Cu, Zn) diketonates on oxidation of sunflower-seed oil with atmospheric oxygen was studied.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Top Picks: new discover of Bis(acetylacetone)copper

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A process for the preparation of the nitrile compound of the carbonitriding method (by machine translation)

The present invention provides a method for the preparation of nitrile compounds cyanide, the organic halide or to be halide with a readily available and inexpensive CO2 , NH3 And a reducing agent, in the presence of a transition metal catalyst of selective carbonitriding reaction, to obtain the target product with a nitrile compound. In the present invention using a brand-new reaction route, through the metal catalytic CO2 And the NH3 The reaction, “one-pot” directly realize halide and intended to halide removing (intended to be) […], avoids the need to use the traditional cyano reaction equivalent highly toxic cyanide issues, at the same time provides a direct, the new method of preparing isotope-labeled nitrile compounds, can be used for medical, tracing, in biological and pharmaceutical research. (by machine translation)

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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CuFeS2 colloidal nanocrystals as an efficient electrocatalyst for dye sensitized solar cells

Cubic CuFeS2 nanocrystals (NCs) have been obtained via a facile colloidal chemistry approach and they show remarkable catalytic activity in the reduction of I3-. Dye sensitized solar cells (DSSCs) with CuFeS2 NCs as counter electrodes (CEs) display a power conversion efficiency of 8.10% comparable to that of a cell with Pt as the CE (7.74%) under the same conditions.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Reaction of the framework 3d-organometallosiloxanes with acetylacetone

A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO2]6M 6[PhSiO2]6, where M = Cu, Ni, Mn, was studied by GPC, 1H and 29Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)2. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO2]6M6[ThSiO2]6. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]6, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by 29Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with 1H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)2 has been accomplished for the first time.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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PROCESS FOR THE PREPARATION OF METAL ACETYLACETONATES

The present invention provides an improved, economical and environmmentally benign process for metal complexes of acetylacetone having the general formula, M(acac)n wherein M is a metal cation selected from the group consisting of Fe, Co, Ni, Cu, Zn, Al, Ca, Mg, Mo, Ru, Re, U, Th, Ce, Na, K, Rb, Cs, V, Cr, and Mn etc., n is an integer which corresponds to the electrovalence of M, are obtained by reacting the corresponding metal hydroxide, metal hydrated oxide or metal oxide with a stoichiometric amount of acetylacetone and separating the product.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Compositionally tunable photoluminescence emission in Cu 2ZnSn(S1-xSex)4 nanocrystals

Inorganic nanostructures: Alloyed Cu2ZnSn(S1-xSe x)4 wurtzite nanocrystals (10nm in size) with a varying composition (x=0-1) were synthesized using a colloidal hot injection route. A photoluminescence (PL) emission study of these nanocrystals shows a compositionally tunable band-gap ranging between 0.9-1.4eV that directly correlates to the sulfur-to-selenium ratio (see picture). Copyright

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Structure of bis[ethyl (trifluoroacetyl)acetato]copper(II) and its adduct with 4-(dimethylamino)pyridine: EPR and X-ray study

Bis[ethyl (trifluoroacetyl)acetato]copper(II), [Cu(etfac)2], has been prepared and studied by X-ray crystallography and EPR spectroscopy. The complex is centrosymmetrical and crystallizes in the P21/c space group with two formula units per unit cell. After dissolving of the complex in solid matrix or in suitable solvents some changes are detected in the EPR spectra and are discussed. The EPR spectra of the complex magnetically diluted in the corresponding Pd(II) complex reveal the presence of only one paramagnetic species further denoted as B. However, EPR spectra measured in solution indicate the presence of two different paramagnetic species: (i) non-distorted parent species B, and (ii) rhombic-distorted species A, which prevail in solutions. The A:B species ratio is a function of the solvent and temperature. The [Cu(etfac)2] adduct with 4-(dimethylamino)pyridine has also been studied and found to crystallize in the C2/c space group. The adduct EPR spectrum monitored in solution shows the presence of only one paramagnetic species.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Synthesis of Ba2YCu3O7-delta Superconductor through Organometallic Route

The chemical synthesis of a high-Tc Ba2YCu3O7-delta superconductor was investigated through the organometallic route, using Ba metal, Y(OPri)3, and Cu-alkoxides or Cu-acetylacetonate as starting materials.Chemically homogeneous submicron powders of single phase Ba2YCu3O7-delta were successfully prepared at 750 deg C by controlled partial hydrolysis metal alkoxides.The utilization of ozone for favorable decomposition of Ba2YCu3O7-delta precursors was found to have a remarkable effect on suppressing the formation of Ba CO3 and lowering the formation temperature of Ba2YCu3O7-delta to about 650 deg C.The single phase Ba2YCu3O7-delta ceramics exhibited superconductivity at approximately 83 K (Tc end).

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”