Archives for Chemistry Experiments of 13395-16-9

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Synthesis and crystal structure of tetra- and hexanuclear uranium(IV) complexes with hexadentate compartmental Schiff-base ligands

Treatment of UCl4 with the hexadentate Schiff bases H 2L? in thf gave the expected [UL?Cl2(thf)] complexes [H2L? = N,N?-bis(3-methoxysalicylidene)-R and R = 2,2-dimethyl-1,3-propanediamine (i = 1), R = 1,3-propanediamine (i = 2), R = 2-amino-benzylamine (i = 3), R = 2-methyl-1,2-propanediamine (i = 4), R = 1,2-phenylenediamine (i = 5)]. The crystal structure of (UL4Cl 2(thf)] (4) shows the metal in a quite perfect pentagonal bipyramidal configuration, with the two Cl atoms in apical positions. Reaction of UCl 4 with H4L? in pyridine did not afford the mononuclear products [U(H2L?)Cl2(py)x] but gave instead polynuclear complexes [H4L? = N,N?-bis(3-hydroxysalicylidene)-R and R = 1,3-propanediamine (i = 6), R = 2-amino-benzylamine (i = 7) or R = 2-methyl-1,2-propanediamine (i = 8)]. In the presence of H4L6 and H4L7 in pyridine, UCl4 was transformed in a serendipitous and reproducible manner into the tetranuclear U(IV) complexes [Hpy]2[U 4(L6)2(H2L6) 2Cl6] (6a) and [Hpy]2[U4(L 7)2(H2L7)2Cl 6][U4(L7)2(H2L 7)2 Cl4(py)2] (7), respectively. Treatment of UCl4 with [Zn(H2L6)] led to the formation of the neutral compound [U4(L6) 2(H2L6)2Cl4(py) 2] (6b). The hexanuclear complex [Hpy]2[U 6(L8)4Cl10(py)4] (8) was obtained by reaction of UCl4 and H4L8. The centrosymmetric crystal structures of 6a¡¤2HpyCl¡¤2py, 6b¡¤6py, 7¡¤16py and 8¡¤6py illustrate the potential of Schiff bases as associating ligands for the design of polynuclear assemblies.

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

 

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Copper(II) and nickel(II) complexes of binucleating macrocyclic bis(disulfide)tetramine ligands

Novel macrocyclic bis(disulfide)tetramine ligands and several Cu(II) and Ni(II) complexes of them with additional ligands have been synthesized by the oxidative coupling of linear tetradentate N2S2 tetramines with iodine. Facile demetalation of the Ni(II) oxidation products affords the free 20-membered macrocycles meso-9 and rac-9 and the 22-membered macrocycle 16, all of which are potentially octadentate N4S4 ligands. X-ray structure analyses reveal distinctly different conformations for the two isomers of 9; meso-9 shows a stepped conformation in profile with the disulfide groups corresponding to the rise of the step, whereas rac-9 exhibits a V conformation with the disulfide groups near the vertex of the V. No metal complexes of rac-9 have been isolated. Crystallographic studies of three Cu(II) complexes reveal that depending upon the size of the macrocyclic ligand and the nature of the additional ligands (I-, NCO-, and CH3CN), the Cu(II) coordination geometry shows considerable variation (plasticity), with substantial changes in the Cu(II)-disulfide bonding. Thus, a diiodide salt contains six-coordinate Cu(II) to which all four bridging disulfide sulfur atoms form strong equatorial bonds. In contrast, isocyanato complexes of the 20- and 22-membered macrocycles exhibit trigonal-bipyramidal Cu(II) and distorted cis-octahedral Cu(II) geometries, respectively, having only one and no short equatorially bound sulfur atoms. The coordination geometry of the latter complex can also be described as four-coordinate seesaw with two semicoordinated S(disulfide) ligands. Disulfide ? Cu(II) ligand-to-metal charge transfer absorptions of both isocyanato-containing Cu(II) species appear too weak to observe, probably because of poor overlap of the sulfur orbitals with the Cu(II) d-vacancy. The dual disulfide-bridged Ni(II) units of the crystallographically characterized octahedral Ni(II) complex of meso-9 with axial iodide and acetonitrile ligands promote substantial antiferromagnetic coupling (J = -13.0-(2) cm-1).

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

 

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Low temperature phase selective synthesis of Cu2ZnSnS 4 quantum dots

The application of indium-free quaternary chalcogenides, such as Cu 2ZnSnS4 (CZTS), in photovoltaics has created tremendous interest in recent years. In this paper we develop a method to synthesize high quality CZTS nanoparticles with thermodynamically stable kesterite and wurtzite phases via a simple, one-pot, low-cost solution method.

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

 

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.Product Details of 13395-16-9, Name is Bis(acetylacetone)copper, molecular formula is C10H16CuO4, Product Details of 13395-16-9. In a Article, authors is Eisch, John J.£¬once mentioned of Product Details of 13395-16-9

Skeletal rearrangements of arylborane complexes mediated by redox reactions: thermal and photochemical oxidation by metal ions

A variety of metal salts have been found to undergo reduction by thermal and photochemical interaction with tetraarylborate salts and with neutral alkyl- and aryl-borane complexes.In the cases of Cu2+, Cu+, Ni2+, Co2+, Pd2+, Pt2+, Ag+, Zn2+, Hg2+, Sn2+, Pb2+ and Rh3+ salts, such photochemical reductions with NaBPh4 led to the deposition of the free metal, while a number of binary mixtures of metal salts led to the codeposition of both metals, sometimes as true alloys, under such photoreduction.In the course of these reductions the arylboratereductants underwent oxidative coupling of the aryl groups to form biaryls in a strictly intra-ionic (for BAr4-) or intramolecular (Ar3B) manner respectively.Individual studies of the photochemistry of the tetraarylborate anion itself, of cuprous tetraphenylborate and of the triphenylborane-pyridine complex have adduced evidence for a gamut of reactive intermediates capable of serving as the photoreductant for metal ions, such as triarylborane radical anions, diarylborate(I) anions or arylborenes, 7-borabicycloheptadiene anions or neutral complexes and finally arylborohydride anions or arylboron hydrides.The role of these intermediates both in the photoinduced skeletal rearrangements of arylboranes and in the concomitant reduction of metal ions is discussed in critical detail.Key words: Boron; Aryl; Oxidation; Copper; Nickel; Zinc

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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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Photoelectron spectra of gamma-substituted nickel(II) and copper(II) bis(acetylacetonates)

The electronic structures of Ni(II) and Cu(II) bis(acetylacetonates) and some of their gamma-substituted analogues (X = Cl, Me) are studied by photoelectron spectroscopy (PES). The vertical ionization energies of the compounds are determined, and the spectra are interpreted based on the trends of changes in the electronic structure and photoelectron spectra of acetylacetonates upon gamma-substitution. The suggested interpretation of the photoelectron spectra is confirmed by the quantum chemical INDO calculations of the electronic structure of the Cu(II) compounds.

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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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Condensed, solution and gas phase behaviour of mono- and dinuclear 2,6-diacetylpyridine (dap) hydrazone copper complexes probed by X-ray, mass spectrometry and theoretical calculations

We describe the synthesis of novel mononuclear and dinuclear copper complexes and an investigation of their behaviour in solution using mass spectrometry (ESI-MS and ESI-MS/MS) and in the solid state using X-ray crystallography. The complexes were synthesized from two widely used diacetylpryridine (dap) ligands, i.e. 2,6-diacetylpyridinebis(benzoic acid hydrazone) and 2,6-diacetylpyridinebis(2-aminobenzoic acid hydrazone). Theoretical calculations (DFT) were used to predict the complex geometries of these new structures, their equilibrium in solution and energies associated with the transformations.

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

 

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Reactions of alpha,beta-Enones with Diazo Compounds: Part 4: Reaction Pathways from (Z)- and (E)-alpha,beta-Enones with Dimethyl Diazomalonate

In this study, (E)- and (Z)-enones carrying only a phenyl substituent at their C(beta) atom were treaced with dimethyl diazomalonate in the presence of (acetylacetonato)copper(II). According to the configuration of the starting enones, the products were dioxole or dihydrofuran derivatives, significant heterocycles in natural products.

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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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The “one-pot” synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone over PdCu catalysts prepared from layered double hydroxides

Supported PdCu catalysts prepared from layered double hydroxides (LDHs) as precursors were evaluated in the gas phase reaction of acetone with hydrogen to methyl isobutyl ketone (MIBK). Two series of catalysts containing ca. 0.2 wt.% Pd and various amounts of Cu (Cu/Pd molar ratio of ca. 0.25, 0.5 and 1) were elaborated according to different methods. One series of precursors was obtained by impregnation of calcined Mg(Al)O mixed oxide with heterobinuclear Pdx Cu1-x acetylacetonates. A second series of precursors was synthesized by coprecipitation of Mg/Pd/Cu/Al LDHs. After calcination, both series were reduced at 473 K. The extends of basic, acid and metal functions were evaluated through microcalorimetric adsorption of CO2, TPD of NH3 and TPR of H2. It was found that the multifunctional transformation of acetone to MIBK was rate determined by the basic function. However, the way by which the catalysts were prepared, impregnation or coprecipitation, controls the extend of hydrogenated by-products, isopropyl alcohol and 4-methyl-2-pentanol. The extensive dilution by migrating MgAlOx species onto the metallic particles makes the coprecipitated catalysts highly selective by decreasing selectively the rate of C=O bond hydrogenation.

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

 

Brief introduction of Bis(acetylacetone)copper

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Stereocontrol in a ytterbium triflate-catalyzed 1,3-dipolar cyclo-addition reaction of carbonyl ylide with N-substituted maleimides and dimethyl fumarate

The addition of Yb(OTf)3 (10 mol%) in a Rh2(OAc)4-catalyzed reaction of o-(methoxycarbonyl)-alpha-diazoacetophe-none with N-methylmaleimide in CH2Cl2 or in diethyl ether gave cycloadducts with high endo-selectivity (endo:exo = 95:5-96:4). The CuOTf (20 mol%)-or CuCl-Yb(OTf)3 (5 mol%)-catalyzed reaction also gave 1,3-dipolar cycloadducts in an endo-selective manner (endo:exo = 94:6). On the other hand, a reaction using only Rh2(OAc)4 (5 mol%) as the catalyst in benzene under reflux gave cycloadducts with exo-selectivity (endo:exo = 11:89). The reaction of N-ethyland N-phenylmaleimides under the same conditions showed a similar tendency in terms of the stereoselectivity.

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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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Laser induced electroactivity of polyamide composites

There were studied polyamide composites containing copper(II) oxide (CuO) and copper(II) acetoacetate Cu(acac)2, which after laser irradiation became fully prepared for an electroless metallization process. The composites were produced by use of typical processing methods such as extrusion and injection moulding. They were then irradiated with various numbers of ArF excimer laser pulses (lambda = 193 nm) at different fluences. The metallization procedure of the laser-irradiated samples was performed by use of a commercial metallization bath and formaldehyde as a reducing agent. The samples were examined using the FTIR and XPS techniques. Examinations were focused on elucidation of possible chemical reactions between CuO and Cu(acac)2, affected by both thermal processing and laser irradiation. It was found that CuO was efficiently reduced to Cu(0) and that surface became highly active for the direct electroless metallization. A chemical reaction model for this reduction is proposed as well.

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