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.

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.

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.

Study on copper complexing ligand concentrations in several China's coastal waters

Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows： Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer （SSL） in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complex- ing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China＇s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.

Triangle Type Trinuclear Copper Complexes with Triplet-excitation Luminescent Property, an Ab Initio Study

The luminescent mechanism and properties of a triangular Cu（I） complex, （CuPz）3. have been studied by CIS method. The ground and lowest triplet excitation state geometries were optimized at MP2/SBKJC and CIS/SBKJC levels, respectively. A remarkable geometry distortion of the lowest triplet state was found and believed to cause the emission spectra to red shift.

Synthesis and Structural Characterization of a Copper Complex with Furaldehyde Salicylylhydrazone

The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P211n with a = 5.9765（3）, b = 15.7196（9）, c = 12.0514（6）A,β= 101.618（3）^o, V = 1109.0（1）A^3, C24H18CuN4O6, Mr = 521.96, Z = 2, Dc = 1.563 g/cm^3, μ = 1.035 mm^-1, F（000） = 534, R = 0.0373 and wR = 0.1058 for 2283 observed reflections （I 〉 2σ（I））. The copper atom has a square-planar CuN2O2 coordination and should be in an octahedral coordination if considering Cu-O （phenol） with distances of 2.796（2）A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O （phenol） bonds, resulting in an extended 1D chain. The title compound exhibits paramagnetic property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.

Synthesis,Structure and Properties of a Binuclear Copper Complex [Cu(Br_2hama)(DMF)]_2,where Br_2hamaH_2=[(3,5-Dibromo-2-hydroxybenzyl-idene)-amino]-methanesulfonic Acid

The copper（II） compound [Cu（Brzhama）（DMF）]2 （C22H24Br4Cu2N4O10S2, Br2hamaH2 = [（3,5-dibromo-2-hydroxybenzylidene）-amino]-methanesulfonic acid, DMF = N,N＇-dimethylformamide） 1 crystallizes in trictinic, space group P1 with a = 8.477（2）, b = 10.164（2）, c = 10.671（2）A, α= 112.66（3）, β = 104.33（3）, γ = 96.67（3）°, Z = 1, and R = 0.0789 for 1823 observed reflections with I 〉 2σ（I）. The centrosymmetric molecule comprises a pair of copper atoms connected by two anions of [（3,5-dibromo-2-hydroxybenzylidene）-amino]-methanesulfonic acid in a tetradentate coordination mode. The five-coordination of copper（II） is further completed by DME The complex forms a 1-D chain through C-H…π hydrogen bonds. The Cu^II…Cu^II distance is 4.937（1） A.

ELECTROLYTIC REMOVAL OF COPPER FROM GUANYL-O-ALKYL-ISOUREA COPPER COMPLEX

A facile method for removing copper from guanyl-0-alkylisourea copper complex was found by using electrolysis.The complex was electrolyzed at a copper cathode in dilute hydrochloric or nitric acid to give guanyl-O- alkylisourea salt in high yield and current efficiency.

Synthesis, Structure and Properties of a Copper Complex Cu_2(μ-PhCOO)_2(μ-CH_3COO)_2(CH_3OH)_2

The title complex Cu2（μ-PhCOO）2（μ-CH3COO）2（CH3OH）2 1 （C20H24Cu2O10, Mr = 551,47） has been synthesized by the reaction of Cu（OAc）2·H2O with benzoic acid, and its crystal structure was determined by X-ray diffraction method. Complex 1 belongs to orthorhombic, space group Pbca with a = 13.083（6）, b=8.078（4）, c = 21.566（2）A, V= 2279（2） A3, Z = 4, Dc= 1,607 g/cm^3, F（O00） = 1128,μ（MoKα） = 1.918 mm^-1, the final R = 0.0506 and wR = 0.1382. Each Cu（n） ion is coordinated by five oxygen atoms from two benzoic acids, two acetic acids and one methanol molecule in a slightly distorted square pyramidal environment. The title molecules construct a 2-D layer via the hydrogen bonds O-H…O. Solid-state photoluminescent investigation reveals that complex 1 displays strong emissions, IR and TG-DTA studies are also presented.

Determination of copper complexation in surface microlayer of Daya Bay and Jiaozhou Bay

Copper complexing ligands concentration (C C) and conditional stability constant of the sea surface microlayer (SML) and subsurface layer (SSL) samples, collected from Daya Bay of Guangdong Province and Jiaozhou Bay of Shandong Province, were determined by anodic stripping voltammetry (ASV) technique. C C of Daya Bay in the SML ranged from 6.19×10-7 to 3.52×10-7 mol/L. C C of Jiaozhou Bay in the SML ranged from 5.30×10-7 to 3.03×10-7 mol/L in August 1998 and from 3.46×10-7 to 1.36×10-7 mol/L in May 2000. The C C concentrations were higher in all surface microlayer samples, compared with corresponding subsurface samples. The average enrichment factors of copper complexation in the SML observed above were 1.58, 1.41 and 1.56, respectively. The enrichment of C C concentration in the microlayer demonstrated that organic ligands had certain buffer action on the toxicity of the enriched trace metals in the same layer. Conditional stability constants of the SML in Jiaozhou Bay were lower than those of the SSL; however, it showed just opposite for Daya Bay. BOD (biological oxygen demand) and COD (chemical oxygen demand) indicated the organic matter content, also showed enriched in the SML. C C had an obvious relationship with BOD or COD.

Synthesis and Characterization of the Copper Complex Pearlescent Pigment

The copper complex pearlescent pigment was synthesized by the two steps diazotization and azo coupling. The crystal phases and the microstructure of the copper complex pearlescent pigment powders were characterized through a combination of DSC, FT-IR and SEM analysis after purification. The results indicated that the copper complex pearlescent pigment has very good thermal stability and the fine particle size is uniformly distributed, and the average grain size is around 15 μm.

Two Copper Complexes Based on Pyrazole-3-carboxylic Acid as Heterogeneous Catalysts for Highly Selective Oxidation of Alkylbenzenes

Two new copper complexes based on pyrazole-3-carboxylic acid （H2pca） ligand, Cu（Hpca）2（H2O）2？2H2O （1） and Cu2（pca）2（H2O）4 （2） have been synthesized and fully characterized by single-crystal X-ray diffraction （SXRD）, infrared spectroscopy （IR）, thermal gravity analysis （TGA）, powder X-ray diffraction （PXRD） and elemental analyses. Complex 1 is mononuclear while complex 2 shows a dinuclear structure. Complex 1 crystallizes in the monoclinic system, space group P21/c with Z = 2, a = 6.5591（5）, b = 21.696（2）, c = 4.9486（2） ？, V = 680.94（9） ？3, F（000） = 366, Dc = 1.745 g/cm3, μ = 1.650 mm-1, the final R = 0.0340 and wR = 0.0792. Complex 2 crystallizes in the monoclinic system, space group P21/n with Z = 2, a = 5.1935（4）, b = 9.6052（7）, c = 12.7347（9） ？, V = 634.44（8） ？3, F（000） = 420, Dc = 2.195 g/cm3, μ = 3.404 mm-1, the final R = 0.0305 and wR = 0.0653. The three-dimensional frameworks of two complexes are formed by the O？H？？？O and N？H？？？O hydrogen bonding interactions. Notably, two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide （TBHP） as the oxidant and they exhibit excellent catalytic performance （Conv. up to 98.9%, Sele. up to 98.7%）.

Crystal Structure and Electrochemical Behavior of Copper Complex with 6-Hydroxymethyl-substituted Tris(2-pyridylmethyl) Amine, [CuCl(C_(19)H_(20)N_4O)]ClO_4

A Cu(II) complex [CuCl(C19H20N4O)]ClO4 1 containing hydroxymethyl substituted TPA (TPA = tris(2-pyridylmethyl)amine) was prepared. It crystallizes in monoclinic, space group P21/c with a = 11.7628(2), b = 13.0083(3), c = 15.11280(10) ?, β = 108.724(2)°, V = 2190.09(7) ?3, Mr = 518.83, Z = 4, T = 293(2) K, Dc = 1.574 g/cm3, μ = 1.280 mm-1, F(000) = 1060 and S = 1.085. The final R = 0.0543 and wR = 0.1433 for 2693 observed reflections with I >2σ(I). The penta- coordinated copper (II) complex assumes an approximate square pyramidal geometry. Cyclic volta- mmetry measurement of the complex showed a quasi-reversible CuII/CuI redox couple with E1/2 = –0.467 v and ?E = 68 mv.

Synthesis and Structure of a Novel Chain-like Inorganic-organic Hybrid Constructed from Isopolyanion and Oxalato-bridged Dinuclear Copper Complex

A novel inorganic-organic hybrid based on isopolyanion,{[Cu2（phen）2（μ-ox）][H2Mo8O26]}·4EtOH·Et2O（1） （phen=phenanthroline,ox=oxalate）,was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters：a=1.1075（5） nm,b=1.1608（5） nm,c=1.3333（5） nm,α=91.683（5）o,β=113.996（5）o,γ=112.170（5）o,V=1.4159（10） nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F（000）=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-（Mo8O26）4-] and oxalato-bridged dinuclear copper complex cations [Cu2（phen）2（μ-ox）]2＋.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment （CCDC No.665101）.

Molecular Parity Violation of Copper Complexes

Aqua[(6-carboxyl-2-pyridilamide)histaminato]copper(II)1 was synthesized for study of MPV(molecular parity violation).Crystal structure of 1 was defined by X-ray crystallographic analysis to give racemic structure consisting of planar-R(pR)and planar-S(pS)enantiomers.Each enantiomer was square pyramidal five coordinated copper complex with the fifth apical ligand of H2O molecule.Specific rotation of the time development analysis of 1 gave mutarotation phenomenon from pR enantiomer priority side([α ]D:+2,450°)to pS enantiomer priority state([α ]D:-1,240°)in MeOH.Chiral irradiation energy of the detector from outside gave dynamic equilibrium between enantiomers,resulted to give pS enantiomer priority state with dissipative process.MPV of 1 was followed that the parity inversion of chiral restraint dz2 orbital brought about inversion of chiral coordination sphere along z-axis for alternative replacement of the fifth apical ligand to solvent molecule on copper atom.SMPV(spontaneous molecular parity violation)of 1 was observed vice versa on transfiguration of specific rotation from the last pS enantiomer priority state([α ]D:-1,240°)to pR enantiomer priority side([α ]D:+2,450°)without chiral irradiation of optical detector,until reset analysis of the same sample.Therefore,the pR enantiomer priority state had existed in the lowest free energy of the ground state as visually unobservable SMPV state of 1 in the solvent.

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 Structures of Three Hybrid Materials Using Vanadium Polyoxoanions and Macrocyclic Copper Complex as Building Blocks

The reactions of the four-coordinated macrocyclic copper complex [CuL]（ClO4）2（L = 1,4,8,11-tetraazacyclotetradecane） with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O（1）, [CuL]3[V（10）O（28）]·8H2O（2） and [Cu L]3[V6O（18）]·8H2O（3）. Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O（18）]6- ring, [V（10）O（28）]6- cluster, and [V（12）O（35）]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2＋ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O（18）]^6- rings in 1 and [V（12）O（35）]^10- rings in 3 into three-dimensional frameworks, respectively.

Preparation and Properties of Copper Fine Wire on Polyimide Film in Air by Laser Irradiation and Mixed-Copper-Complex Solution Containing Glyoxylic Acid Copper Complex and Methylamine Copper Complex

Formation of copper wiring on a polyimide film by laser irradiation to a stable copper-complex film consisting of glyoxylic acid copper complex and methylamine copper complex in air has been investigated. A stable metallic copper on the polyimide film was precipitated even in air. Since this copper was generated only in the laser-irradiated parts, direct patterning of copper wiring was possible. It was also found that copper was precipitated by electroless copper plating on the laser-deposited copper wiring and it was possible to thicken the copper wiring by this precipitation. The resistivity of the copper wiring was almost the same as that of the bulk of metallic copper. The developed method—combining laser irradiation to a copper-complex-coated film and electroless copper plating—enables the high-speed deposition of fine copper wiring on a polyimide film in air by a printing process, indicating an inexpensive and useful process for fabricating copper wiring without high vacuum facility and heat-treatment under inert gas.

Fabrication of Copper Wire Using Glyoxylic Acid Copper Complex and Laser Irradiation in Air

Preparation of a glyoxylic acid copper complex and fabrication of fine copper wire by CO2 laser irradiation in air to a thin film of that complex have been investigated. Irradiating laser to the complex thin film spin-coated on a glass substrate, thin film of metallic copper was fabricated in areas that were subjected to laser irradiation in air. The thickness of this thin copper film was approx. 30 to 40 nm, and as non-irradiated areas were etched and removed by a soluble solvent of the copper complex, fine copper wire with 200 μm width was formed by laser direct patterning. The resistivity of this thin copper film depended on the irradiation intensity of the laser and was 3.0 × 10–5 Ω·cm at 12 W intensity (sweep speed: 20 mm/s). This method enables the high-speed deposition of copper wiring in air by a printing process, indicating an inexpensive and useful process for fabricating copper wiring.