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

 

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

 

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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”