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Decomposition of the rigid polycyclic beta,gamma-unsaturated diazomethyl ketones (1a) and (1b) and (2a) and (2b) promoted by ‘activated CuO’, Cu(acac)2, Cu(OTf)2, or Ni(acac)2 in the presence of methanol are shown to give mainly the corresponding rearranged gamma,delta-unsaturated angularly substituted esters (3a) and (3b) and (8a) and (8b) together with the alpha-methoxy ketones (4a) and (4b) and (9a) and (9b).While photo-Wolff rearrangement of the diazo ketones leads to the corresponding homologous esters (5a) and (5b) and (10a) and (10b) the silver benzoate-triethylamine induced reaction gives the rearranged esters in addition to the homologous esters.

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

 

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The Cu(phac)2 complex was synthesized by the reaction of copper(II) acetate with acetylacetone phenylhydrazone (Hphac), and its crystal structure was established by X-ray diffraction: space group P21/c, a = 11.173(3) A, b = 8.267(2) A, c = 12.633(4) A, beta = 115.01(3), V = 1057.5(5) A3, Z = 4, R1 = 0.0476. The crystal structure of Cu(phac)2 consists of the centrosymmetrical mononuclear molecules. The central copper(II) ion is coordinated by two oxygen atoms and two nitrogen atoms of two acetylacetone phenylhydrazone ligands. The Cu(phac)2 molecules are linked in layers parallel to the Oyz plane. The oxygen atoms of the ketone fragment are involved in intermolecular bonding, which completes the coordination sphere of the central copper(II) ion to a substantially elongated octahedron. The thermal stability of the Cu(phac)2 complex was estimated under nitrogen at atmospheric pressure and in vacuo.

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

 

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The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing quantitative kinetic, and theoretical assessments of solvent structures and their interactions with reaction intermediates and transition states. 13395-16-9, Name is Bis(acetylacetone)copper, belongs to copper-catalyst compound, is a common compound. Application of 13395-16-9In an article, once mentioned the new application about 13395-16-9.

Superconducting YBa2Cu3O7-delta films were prepared on yttria stabilized zirconia substrates by the dipping-pyrolysis process using metal acetylacetonates (Y/Ba/Cu=1.0/3.0/4.3) as starting materials; Tc(onset) of 97 K and Tc(end) of 89 K were achieved in the resistivity measurement for the films annealed at 950 deg C in O2.

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

 

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

 

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Several mixed ligand complexes of copper(II) and nickel(II) having the compositions and , where aaH is acetylacetone, tcaH is trichloroacetic acid; L is gamma-picoline, imidazole, 2-picoline-N-oxide or thiourea and M is Cu(II) or Ni(II), have been isolated and characterised on the basis of their analyses, molar conductance, magnetic susceptibility, infrared, electronic spectral data and thermogravimetric measurements.The infrared spectra reveal the presence of uninegative bidentate acetyl acetonate and trichloroacetate groups in all these complexes.As the temperature increases, the mixed ligand complexes start decomposing with the loss of neutral donor ligand, followed by trichloroacetate ion and acetylacetonate ion in definite steps and ultimately forming MO at 600-675 deg .Square planar, tetrahedral, distorted octahedral and octahedral structures have been proposed for the complexes, , , and , respectively.

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

 

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The oxidation of alkanes to the corresponding alcohols and ketones and the epoxidation of alkenes can be performed efficiently at room temperature with molecular oxygen (1 atm) in the presence of an aldehyde and a copper salt catalyst such as copper(II) hydroxide. Extremely high turnover numbers have been obtained for the oxidation of cyclohexane using a combination of copper(II) chloride and a crown ether as a catalyst.

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

 

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An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.

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

 

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Copper(II) and cobalt(II) Schiff base complexes with derivatives of the pentadentate ligand bis(salicylideneimino-3-propyl)amine [H2salDPT] have been prepared. The X-ray crystal structures of the copper(II) complexes Cu[salDPT] and Cu[sal(n-propyltrimethylsilyl)DPT] were determined and revealed five-coordination at the metal centre in both cases. The 1:1 dioxygen adduct of Co[sal(n-propyltrimethylsilyl)DPT] was also isolated and its X-ray molecular structure determined.

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

 

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Several compounds have been isolated from the reaction between different copper bis(acetylacetonato) derivatives and the potentially bridging ligand 2,3-bis(2-pyridyl)pyrazine (bppz). A compound of formula [Cu(tfacac) 2(bppz)] (1) is obtained when the substituted trifluoromethylacetylacetonato is used. The use of different anions and the unsubstituted acetylacetonato give rise to new derivatives of general formula [{Cu(acac))2(mu-bppz)2]X2 (X– BF4-, 2; PF6-, 3; BPh 4-, 4). In these compounds the bppz ligand is acting as a bridge by chelating one copper atom and bonding monodentate a second copper atom. The presence of anions with different coordination abilities introduces variations in the copper environment and geometry. When the non-coordinating tetraphenylborate is used different compounds depending on the nature of the solvent are obtained. The dimer 4 was isolated from a methanol/chloroform mixture, while in the absence of chloroform the monomeric compound of formula [Cu(acac)(bppz)(ROH)](BPh4)-ROH (ROH=MeOH, 5) was obtained. When ethanol was used instead of methanol the analogous derivative 6 (R=EtOH) was isolated. Both species show a mononuclear structure with the copper atom five-coordinated by the chelating acac and bppz ligands and one hydroxo group occupying the apical position. A similar environment for the copper appears in [Cu(tfacac)(bppz)(MeOH)](BPh4), 7, which shows a dimeric structure through hydrogen bonds interactions. The magnetic susceptibility data of the dimeric compounds show very weak antiferromagnetic interactions between the copper atoms, an expected fact since the bridging bppz ligand is not planar but the monodentate pyridine is more or less perpendicular to the other two aromatic rings, precluding the spin exchange via the it ligand electrons.

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

 

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The interaction of 2-pyridinecarboxaldehyde with N-tosyl-1,2-diaminobenzene leads to the isolation of two different products, {3-[ethoxy(2-pyridyl)methyl]-1-[(4-methylphenyl)sulfonyl]-2-(2-pyridyl)-2,3- dihydro-1H-benzo[d]imidazole}, L1, and {1-[(4-methylphenyl)sulfonyl]-2-(2-pyridyl)-2,3-dihydro-1H-benzo[d] imidazole}, L2, but not to the expected Schiff base 1-[(4-methylphenyl)sulfonamido]-2-[(2-pyridylmethylene)amino]benzene, HL3. Two kinds of complexes, containing the potentially tridentate and monoanionic [L3]- as a ligand, were obtained by different routes. ML3(p-Tos)(H2O)n complexes (p-TosH = p-toluenesulfonic acid; M = Co, Cu, Zn; n = 1-3) have been isolated by electrolysis of a solution phase composed of L1 and p-toluenesulfonic acid, using metal plates as the anode. Metal complexes of composition ML32(H2O)n (M = Mn, Co, Cu, Zn; n = 0-2) were obtained by template synthesis from M(acac)2, 2-pyridinecarboxaldehyde and N-tosyl-1,2-diaminobenzene. All these compounds have been characterised by elemental analyses, magnetic measurements, IR, mass spectrometry and, in the case of M = Zn, by 1H NMR spectroscopy. CuL3(p-Tos)(H2O), 1, ZnL3(p-Tos)(H2O), 2, CoL32, 3, CuL32, 4 and ZnL32 · 2CH3CN, 5, were also crystallographically characterised.

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