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Monodisperse CuS nanodisks: Lowerature solvothermal synthesis and enhanced photocatalytic activity

Controllable synthesis of uniformly disk-shaped CuS nanostructures with a narrow size distribution was realized by a lowerature (150 C) solvothermal process using polyvinyl pyrrolidone (PVP) as the surfactant. Monodispersed nanodisks of pure CuS phase with an average diameter of ca. 500 nm could be obtained at a specific S/Cu molar ratio (xS/Cu) of raw materials, which was revealed to affect the phase structure and morphology of the product but the influence of PVP content (xPVP) is limited. The CuS nanodisks have a broad absorption in the visible region and superior photocatalytic performances for the degradation of RhB whose decomposition rate reaches 93% in 2 h, indicating a potential application in the field of wastewater treatment.

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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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Copper(I) thiocyanate coordination polymers with dimethylpyrazine: Synthesis, crystal structures, thermal and luminescence properties

The new copper(I) coordination polymers polyl(di-mu 2-thiocyanato-N,S)-(mu2-2,5-dimethylpyrazine-N,N)] dicopper(I) (I) and poly[di-mu2-thiocyanato-N,S)-(mu 2-2,3-dimethyl-pyrazine-N,N)] dicopper(I) (II) were prepared by the reaction of copper(I) thiocyanate with 2,3- and 2,5-dimethylpyrazine in acetonitrile. In all compounds different CuSCN sub-structures are found which are connected by the dimethylpyrazine ligands to multi-dimensional coordination networks. The thermal properties of all compounds were investigated using simultaneous differential thermoanalysis (DTA), thermogravimetry (TG) and mass spectrometry (MS) as well as temperature resolved X-ray powder diffraction, On heating, compound I and II loose all of the dimethylpyrazine ligands in an endothermic reaction and transform directly into copper(I) thiocyanate. Optical investigations show two excited states for both compounds in absorption and in luminescence measurements which are both, MC and LMCT in character.

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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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Monomere Alkin-stabilisierte Kupfer(I)-Halogenid- und Kupfer(I)-Pseudohalogenid-Verbindungen; Kristallstructur von <(eta5-C5H4SiMe3)2Ti(C<*>CPh)2>CuCl

The reaction of Me3SiC<*>CSiMe3 (1), LnMC<*>CSiMe3 (4a, LnM = Cp(CO)2Fe; 4b, LnM = Cp(CO)3Mo> and E(C<*>CR)2 (6, E = Me2Si; 8, E = (eta5-C5H4SiMe3)2Ti; R is a singly bonded organic ligand) with CuX (2) (X is a halide or pseudohalide) is described. 1 and 4 react with CuX (2a, X = Cl; 2b X = Br; 2c, X = I; 2d, X = OSO2CF3) to yield the dimeric compounds <(eta2-Me3SiC<*>CSiMe3)CuX>2 (3a, X = Cl; 3b, X = Br; 3c, X = I; 3d, X = OSO2CF3) or <(eta2-LnMC<*>CSiMe3)CuX>2 (5a, LnM = Cp(CO)2Fe, X = Cl; 5b, LnM = Cp(CO)3Mo, X = Cl) respectively.In these compounds the C2 building block is eta2-coordinated to a CuX moiety and by the formation of copper-X-bridges (Cu2X2) a dimer is formed.However, the reaction of Me2Si(C<*>CSiMe3)(C<*>CR) (6a, R = SiMe3; 6b, R = H) with CuX (2) (X = Cl, Br, OSO2CF3, O2CMe) affords polymeric CSiMe3)(eta2-C<*>CR)Cu2X2>>n (7a, R = SiMe3, X = Cl; 7b, R = SiMe3, X = Br; 7c, R = H, X = Cl; 7d, R = H, X = Br; 7e, R = SiMe3, X = OSO2CF3; 7f, R = SiMe3, X = O2CMe) in high yields.In 7a-7f each alkynyl fragment is eta2-coordinated to a CuX unit.While the reaction of 6a or 6b with CuX yields polymeric 7a-7f, the organometallic, 1,4-diyne RC<*>C--C<*>CR ( = (eta5-C5H4SiMe3)2Ti; 8a, R = Ph; 8b, R = SiMe3) affords with CuX (2a, X = Cl; 2b, X = Br; 2c, X = I; 2e, X = CN; 2f, X = SCN) the dinuclear compounds <(eta5-C5H4SiMe3)2Ti(C<*>CR)2>CuX (9a, R = Ph, X = Cl; 9b, R = SiMe3, X = Cl; 9c, R = SiMe3, X = Br; 9d, R = SiMe3, X = I; 9e, R = SiMe3, X = CN; 9f, R = SiMe3, X = SCN).Compounds 9a-9f feature a monomeric copper(I) halide or copper(I) pseudohalidemoiety, which is stabilized by the chelating effect of the alkynyl ligands on (C<*>CR)2. <(eta5-C5H4SiMe3)2Ti(C<*>CSiMe3)2>CuCl (9b) reacts with AgX (X = CN, SCN, O2CMe, O2CPh) to yield <(eta5-C5H4SiMe3)2Ti(C<*>CSiMe3)2>CuX (9e, X = CN; 9f, X = SCN; 9g, X = OC(O)Me; 9h, X = OC(O)Ph) by precipitation of AgCl.In addition, the bis(alkynyl)-ansa-titanocene <(eta5-C5H4)Me2Si(eta5-C5H3SiMe3)>Ti(C<*>CSiMe3)2 (10) yields with CuCl (2a) the dinuclear species <Ti(C<*>CSiMe3)2>CuCl (11).The identity of compounds 3, 5, 7, 9 and 11 is confirmed by analytical and spectroscopic (IR, MS, 1H, 13C NMR) data, and that of <(eta5-C5H4SiMe3)2Ti(C<*>CPh)2>CuCl (9a) is confirmed by X-ray analysis.Crystals of 9a are monoclinic, space group Pc with cell constant a = 992.6(7), b = 1210(1), c = 1335.5(7) pm, beta = 105.75(5) deg, V = 1543(2)x106 pm3 and Z = 2.Keywords: Alkynes, 1,4-Diynes; Copper(I) halides; Copper(I) pseudohalides

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

 

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Construction of [(eta5-C5Me5)MoS 3Cu3]-based supramolecular assemblies from the [(eta5-C5Me5)MoS3(CuNCS) 3]- cluster anion and multitopic ligands with different symmetries

The assembly of a new family of [(eta5-C5Me 5)MoS3Cu3]-supported supramolecular compounds from a preformed cluster [PPh4][(eta5-C 6Me5)MoS3(CuNCS)3]¡¤DMF (1¡¤DMF) with four multitopic ligands with different symmetries is described. Reactions of 1 with 1,2-bis(4-pyridyl)ethane (bpe) (Cs symmetry) or 1,4-pyrazine (1,4-pyz) (D2h symmetry) in aniline gave rise to two polymeric clusters {[{(eta5-C5Me 5)MoS3Cu3}2(NCS)3(mu- NCS)(bpe)3]¡¤3aniline}n (2) and [(eta5- C5Me5)MoS3Cu3(1,4-pyz)(mu-NCS) 2]n (3). On the other hand, solid-state reactions of 1 with 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) (D3h symmetry) or 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphyrin (H2tpyp) (D 4h symmetry if 21H and 23H of the H2tpyp are omitted) at 100C for 12 h followed by extraction with aniline yielded another two polymeric clusters {[(eta5-C5Me5)MoS 3Cu3(tpt)(aniline)(NCS)2]¡¤0. 75aniline¡¤0.5H2O}n (4) and {[(eta5- C5Me5)MoS3Cu3(NCS)(mu-NCS)(H 2tpyp)0.4(Cu-tpyp)0.1] ¡¤2aniline¡¤2.5benzene}n (5). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and X-ray analysis. Compound 2 consists of a 2D (6,3) network in which [(eta5-C5Me5)MoS3Cu3] cores serve both a T-shaped three-connecting node and an angular two-connecting node to interconnect other equivalent units through single bpe bridges, double bpe bridges, and mu-NCS bridges. Compound 3 has a 3D diamondlike framework in which each [(eta5-C5Me5)MoS 3Cu3] core, acting as a tetrahedral connecting node, links four other neighboring units by 1,4-pyz bridges and mu-NCS bridges. Compound 4 contains a honeycomb 2D (6,3)core(6,3)tpt network in which each cluster core, serving a trigonal-planar three-connecting node, links three pairs of equivalent cluster cores via three tpt lignads. Compound 5 has a rare scalelike 2D (4,62)core(42,6 2)ligand network in which each cluster core acts as a T-shaped three-connecting node to link with other equivalent ones through mu-NCS bridges and H2tpyp (or Cu-tpyp) ligands. The results showed that the formation of the four different multidimensional topological structures was evidently affected by the symmetry of the ligands used. In addition, the third-order nonlinear optical properties of 1-5 in aniline were also investigated by using Z-scan techniques at 532 nm.

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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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Copper catalysed oxidation of thiosulfate by oxygen in gold leach solutions

The environmental and public concern over the continued use of cyanide in the recovery of gold has grown in recent times due to a number of recently publicised environmental incidents. Of the alternative lixiviants, thiosulfate appears to be the most promising, though the considerable amount of research conducted on thiosulfate leaching of gold over the last three decades has not resulted in its commercial introduction. Perhaps the largest contributing factor to this is the poor understanding of the thiosulfate leach solution chemistry, especially the oxidation of thiosulfate in the presence of copper(II) and oxygen. It has been shown in this research that the oxidation of thiosulfate in the presence of copper(II) and oxygen is very complex with the rates of copper(II) reduction and thiosulfate oxidation being significantly faster in the presence of oxygen. The higher initial rate of copper(II) reduction indicated that oxygen increases the rate of copper(II) reduction to copper(I) by thiosulfate, though the mechanism for this remains unclear. The rates of thiosulfate oxidation and copper(II) reduction were also shown to be affected differently by the presence of anions. This is consistent with thiosulfate oxidation occurring via two mechanisms, with one of these mechanisms involving the oxidation of thiosulfate by copper(II) and the other involving the oxidation of thiosulfate by the intermediate superoxide and hydroxide radicals formed as a result of copper(I) oxidation by oxygen. The effect of various parameters on the rate of thiosulfate oxidation and the copper(II) concentration are also shown.

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

 

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Theoretical studies on the electronic states of electron-doped copper oxides

The infinite layer copper oxides denoted as ACuO2, where A stands for the alkaline earth metal such as strontium or calcium, have attracted much attention in relation to high-temperature (Tc) superconductivity. Superconductivities of these species are achieved by several chemical doping such as hole-doping (h-doping) and electron-doping (e-doping). In this study, we have performed hybrid-density functional theory calculations, which are available in the strongly correlated systems such as transition metal complexes, in order to examine the electronic states after one e-doping for the linear chain clusters such as CuOCu and Cu3O2. The electronic states have been clarified from view points of energy, spin and charge density populations, natural orbital analysis and the difference of density. As the hole-doped electronic states have already been examined for the same clusters by the same methods in our previous work, we discuss the differences of the changes of electronic states between h-doping and e-doping.

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

 

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Benzothiophene compounds, intermediates, compositions, and methods

The present invention provides a method for inhibiting endometriosis comprising administering to a woman an effective amount of a compound of formula I STR1 wherein R1a is –H or –OR7a in which R7a is –H or a hydroxy protecting group; R2a is –H, halo, or –OR8a in which R8a is –H or a hydroxy protecting group; R3 is 1-piperidinyl, 1-pyrrolidino, methyl-1-pyrrolidinyl, dimethyl-1-pyrrolidino, 4-morpholino, dimethylamino, diethylamino, diisopropylamino, or 1-hexamethyleneimino; n is 2 or 3; and Z is –O– or –S–; or a pharmaceutically acceptable salt thereof.

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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, characterization, and X-ray crystal structures of copper(I) halide and pseudohalide complexes with 2-(2-quinolyl)benzothiazole. Diverse coordination geometries and electrochemical properties

Three new copper(I) complexes with the ligand 2-(2-quinolyl)benzothiazole (qbtz) have been synthesized and characterized by elemental analyses, infrared, and ultraviolet?visible spectroscopy, and their crystal structures have been determined by X-ray diffraction. The coordination geometry around copper in [Cu(qbtz)(mu-I)]2, complex (1), a centrosymmetric dimer, is a distorted CuI2N2 tetrahedron supplemented by a short Cu?Cu interaction of 2.5855 A. The copper(I) cyanide?bridged complex [Cu3(qbtz)2(mu-CN)3] (2) exhibits a one-dimensional chain structure with three crystallographically independent Cu atoms. Two of the copper atoms feature tetrahedral four coordination each by a chelating qbtz ligand and two CN groups, and the third features a quasi-linear two-coordination geometry by two CN. In [Cu(qbtz)(mu-SCN)] (3), copper is in a distorted tetrahedral coordination by two N atoms of a chelating qbtz ligand and by one N atom and one S atom of a bridging SCN group. The complex exhibits a one-dimensional zigzag chain structure with two crystallographically inequivalent Cu atoms in the chain. The spectroscopic and electrochemical properties of compounds 1?3 are in accord with the variation in copper(I) coordination environments.

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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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Seven copper (I) complexes of diphosphine ligands and N^N ligands: Syntheses, structural characterizations and spectroscopic properties

The reactions of diphosphine ligands and nitrogen-containing ligands with Cu(I) salts in the mixed solvents of methanol (MeOH) and dichloromethane (CH2Cl2) generated the corresponding complexes, {[Cu(dppbe)(Bphen)](ClO4)¡¤2CH3OH}n (1), {[Cu2(dppe)(dmp)2(CN)2]¡¤2CH3OH}n (2), {[Cu2(dppb)(dmp)2I2]¡¤2CH3OH}n (3), [Cu(POP)(C16H6N6)]I (4), {[Cu(POP)(C16H6N6)](SCN)}n (5), [Cu(xantphos)(bpy)](ClO4) (6) and {[Cu(xantphos)(bpy)](CF3SO3)}n (7) {dppbe = 1,2-bis(diphenylphosphanyl)benzene, dppe = 1,2-bis(diphenylphosphino)ethane; dppb = 1,4-bis(diphenylphosphino)butane, POP = bis[2-(diphenylphosphino)phenyl]ether, xantphos = 4,5-bis (diphenylphosphio)-9,9-dimethylxanthene, Bphen = 4,7-diphenyl-1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, C16H6N6 = [2,3-f]-pyrazino-[1,10]phenanthroline-2,3-dicarbonitrile, bpy = 2,2?-bipyridine}. These complexes were all characterized by single-crystal X-ray crystallography, elemental analysis, IR, 1H NMR spectroscopy, luminescence and THz spectroscopy. Complexes 1 and 2 consist of 1D infinite zigzag chain structures which are linked by hydrogen bonds, while complexes 3, 5 and 7 have 2D topological architectures which are connected by hydrogen bonds, complex 4 has an annular structure and complex 6 is a mononuclear structure. The types of hydrogen bonds, choice of solvents and coordination modes of the ligands are of importance in defining the structural and topological features of the resulting networks. Furthermore, complexes 1?7 exhibit interesting luminescence in the solid state at room temperature. Complexes 1?3 can act as yellow luminophores, complex 4 acts as a red luminophore, complex 5 acts as an orange luminophore and complexes 6?7 act as green luminophores. Their terahertz spectra show more accurate characteristics of their structures.

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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 OLEFINS WITH A MIXTURE OF IODINE AND MERCURY(II) THIOCYANATE. PREDOMINANT FORMATION OF vic-IODO(ISOTHIOCYANATO)ALKANES.

Treatment of olefins with a mixture of iodine and mercury(II) thiocyanate in benzene or diethyl ether gives vic-iodo(isothiocyanato)alkanes and vic-iodo(thiocyanato)alkanes in a high yield, the former being predominant. Similar results were obtained by using silver(I) and thallium(I) thiocyanates, though both the yield and the selectivity are slightly lower. By use of potassium thiocyanate and copper(I) isothiocyanate in place of mercury(II) thiocyanate, beta -iodo thiocyanates were mainly formed. A reaction scheme involving initial formation of an iodonium ion from olefin and ISCN (formed in situ) and a subsequent attack of complex anion I(SCN)//2** minus has been proposed to account for this predominant formation of beta -iodo isothiocyanates.

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