Catalytic epoxidation of olefin over supramolecular compounds of molybdenum oxide clusters and a copper complex

The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.

Effects of binuclear copper(Ⅱ)threonine complex on blood glucose, lipids and protection of the hearts and kidneys in diabetic mice

Aim To study the effects of binuclear copper （Ⅱ） threonine complex （Cu2 （Thr）4） as analogue of superoxide dismutase （SOD） on blood glucose, blood lipids and vessels of hearts and kidneys in diabetic mice. Methods Diabetic mouse model was established by intraperitioneal injection of alloxan. Low, middle, and high doses of Cu2（Thr）4 at 0.002%, 0.02% and 0.1% were given respectively to diabetic mice following lavage. The fasting blood glucose was determined after the diabetic mice were given Cu2 （Thr）4 for 0, 30, and 45 d. The diabetic mice were killed on the 45th day. Then glycosylated hemoglobin （HbAlc） and blood lipids were assayed, and pathologic changes in hearts and kidneys stained with HE were observed. Results Compared with the control group in which the diabetic mice were given distilled water, the value of blood glucose reduced significantly in middle dose group （P 〈 0.01 ）, followed by that in low dose group （P 〈 0.05）. TC level reduced markedly and HDL level increased significantly in all three treatment groups （P 〈 0.05）. Especially in middle dose group, cardiac muscle fibers were neatly arranged, nucleus and cytoplasm well distributed, glomeruli showing normal structure, cells well distributed and staining being normal. Conclusion Cu2 （Thr）4 reduces blood glucose, regulates blood lipids, and play protective action on the vessels of hearts and kidneys in diabetic mice. The effects of it in middle dose were better than those of other doses.

Hydrothermal Synthesis and Structure of a Copper(II) Complex, [Cu(4,4'bpy)(H_2O)_3]SO_42H_2O

The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

Synthesis, structure, DNA binding and cleavage activity of a new copper(II) complex of bispyridylpyrrolide

A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.

Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid)

The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

Rapid, Catalytic Hydrolysis of DNA by Copper(Ⅱ) Complexes

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Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of the Copper(II) Complex [Cu_4O_4(phen)_4(ClC_6H_4COO)_2(H_2O)_2]·(H_2O)_3

The title complex of copper（Ⅱ） with m-chlorobenzoic acid, 1,10-phenanthroline （phen） and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex： triclinic, space group PI^-, a = 1.06853（12）, b = 1.30740（16）, c = 1.49546（17） nm, α= 101.791（2）,β = 103.413（2）, γ = 105.815（2）°, V= 1.8736（4） nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7（000） = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate： molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.

Effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores

The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.

Synthesis,Crystal Structure and Antibacterial Activity of a New Ternary Copper(Ⅱ) Complex with 2,6-Pyridinedicarboxylic Acid and 1,10-Phenanthroline

A new ternary copper（Ⅱ） complex, [C43H27Cu2N7O5][C14H6CuN2O8]＇6.5H2O, has been synthesized by the reaction of copper sulfate, 2,6-pyridinedicarboxylic acid and 1,10- phenanthroline （phen）, and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. It crystallizes in triclinic, space group P1, with a = 14.379（5）, b = 15.510（5）, c = 15.835（6） A, a = 78.567（6）, β = 63.594（6）, y = 81.287（6）°, V= 3092.1（19） A3, C57H46Cn3N9O19.5, Mr = 1359.54, Z = 2, Dc = 1.446 Mg/m3, λ（MoKa） = 0.71073 A,μ = 1.101 mm^-1, F（000） = 1362, S = 1.071, the final R = 0.0718 and wR = 0.11960 for 10705 observer reflections （I 〉 2σ（I））. The structure unit of the title complex consisfs of a mononuclear part and a di-nuclear part, and the three copper ions show three coordination modes. Each 6-coordinated geometry of the Cu atom is a distorted octahedral coordination geometry. The 3D supramolecular system is formed by the hydrogen bond O-H-O and π-π stacking interaction between neighboring single cells. The antibacterial activity of the title complex is also studied.

Synthesis and Crystal Structure of a Copper(II) Complex with 2,4-Dihydroxybenzylidene Benzoylhydrazone Ligand

A new copper（Ⅱ） complex with formula CuL（py）, where L^2- is the dianion of 2,4-dihydroxybenzylidene benzoylhydrazone, has been synthesized and characterized by IR spectra and single-crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P2 1/c with a=0.9630（4）, b=1.4808（6）, c=1.2320（5） nm, β=104.969（6）°, V=1.6973（Ⅱ） nm^3, Z=4, Dc=1.553 g/cm^3,μ（MoKa）=1.311 mm^-1, F（000）=812, R=0.0694 and wR=0.1727 for 1511 observed reflections （I〉2σ（I））. The crystal structure analysis indicates that the copper（Ⅱ） ion lies in a distorted square-planar environment composed of two oxygen atoms, one nitrogen atom from the tridentate acylhydrazone Schiff base ligand L^2- and one nitrogen atom from the pyridine ligand. Two adjacent molecules are connected via weak Cu…O bonding interactions to form dimers, which are further linked to generate a two-dimensional layer structure via interdimeric hydrogen bonds.

Synthesis and Crystal Structure of the Copper Complex {[Cu(CH_3COO)_2(bbtz)](H_2O)_2}_n

The new copper complex { [Cu（CH3COO）2（bbtz）]（H2O）2 }, 1 （bbtz = 1,4-bis（ 1,2,4- triazol-1-ylmethyl）benzene） was synthesized and the structure was determined by single-crystal X-ray diffraction. Crystal data： C16H22CuN6O6, monoclinic, space group P21/n, a = 12.589（5）, b = 6.455（2）, c = 12.677（5） A, β= 98.748（9）°, V= 1018.2（7） A^3, Mr = 457.95, Z = 2, Dc= 1.494 g/cm^3, F（000） = 474, μ = 1.118 mm^-1, R = 0.0463 and wR = 0.0939 for 1971 observed reflections with I 〉 2σ（I）. The crystal structure of 1 is a one-dimensional chain via the bridging flexible ligand bbtz.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper(Ⅱ) Complex:[Cu_6(DPPZ)_4(btc)_4(H_2O)_8]·5H_2O

A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.

Synthesis and Structural Characterization of a Tetranuclear Copper Complex with 2-Amino-1,3-thiazole

The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.

Synthesis,Crystal Structure and Biological Activity of a Planar Copper Complex Derived from S-benzyldithiocarbazate

A planar transition metal complex Cu（L）2 （L = （E）-benzyl-2-（4-nitrobenzylidene）-hydrazinecarbodithioate） has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system,space group P21/c with a = 6.7101（11）,b = 16.952（3）,c = 13.962（3） ,β = 92.458（4）°,V = 1586.7（5） 3,Z = 4,Mr = 724.33,Dc = 1.516 g·m-3,μ = 0.998 mm-1,F（000） = 742,S = 1.021,R = 0.0634 and wR = 0.1077 for 813 observed reflections with Ⅰ〉 2σ（Ⅰ） and 205 parameters. In the molecular structure of the title complex,the copper atom exhibits a slightly distorted square-planar geometry in which the basal plane is defined by two N and two S atoms from two bidentate ligands. The complex was evaluated for its antitumor activity against two kinds of cell lines （MKN45 and HepG2） by MTT method. The preliminary bioassay indicates that the complex exhibits weak antitumor activity.

Synthesis, Crystal Structure and Properties of a Copper Complex with the Bicycle[2.2.1]-2-heptene-5,6-dicarboxylic Acid

A new copper complex 2{Cu（C10H8N2）[C8H11O2（COO）]（H2O）3}·（H2O）5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid（H2L） [C7H8（COOH）2], basic copper carbonate and 2,2＇-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a = 7.4626（5）, b = 11.9779（8）, c = 12.9841（8）A, α = 109.7040（10）, β = 98.7550（10）, γ = 90.6240（10）°, V = 1077.50（12）A3, Dc = 1.538 g/cm^3, Z = 1, F（000） = 520, GOOF = 1.065, R = 0.0360 and wR = 0.0950. The copper ion is coordinated with four oxygen atoms from one H2 L molecule and three water molecules together with two nitrogen atoms from the 2,2＇-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.