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%）.

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.

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.

The Influence of Pore Structures and Degree of Cross-Linking on Catalytic Properties of Aminomethyl Polystyrene Resin Supported Dendritic Copper Complexes

1 Introduction Immobilization of homogeneous catalysts onto polymer supports through covalent attachment has received wide attention because these materials offer advantage features of heterogeneous catalysis to homogeneous systems.The polymer-supported catalysts enhance their thermal stability,selectivity,recyclability and easy separation from reaction products leading to the operationally flexible[1-2].Such behaviour prompted us to know the effect of pore structures of polymer supporters on catalytic ...

Synthesis and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co（Ⅱ） acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu（Ⅱ） chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Co3（C51H66N3O16）]2（OAc）, monoclinic, space group P21, a = 15.022（3）, b = 14.242（3）, c = 28.922（6） A, β = 98.944（4）°, V = 6112（2） A3, Z = 4, Dc = 1.339 g/cm^3, the final R = 0.0860 for 21906 observed reflections with I 〉 2（I）. For Ⅱ： Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861（13）, b = 20.838（4）, c = 28.274（6） , V = 3644.6（13） 3, Z = 4, Dc = 1.310 g/cm^3, the final R = 0.0642 for 11106 observed reflections with I 〉 2（I）. The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.

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

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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.

Synthesis and Crystal Structures of the α and β Forms of Bis(salicylaldoxime)copper(Ⅱ) Complexes

Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.

Characterization and Crystal Structures of Two Copper(Ⅱ) Complexes Constructed by a Flexible Double Betaine Ligand

A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.

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.

Synthesis,Structural Characterization and Catalytic Activity of Copper(Ⅰ)Complexes with Triphenylphosphine and Pyridine Derivatives

Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945（7）, b = 37.266（2）, c = 10.9461（7） A, β = 116.0750（10）°, V = 3625.3（4） A^3, Z = 4, D_c = 1.350 Mg/cm^（-3）, μ = 0.801 mm^（-1）, F（000） = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections（I 〉 2σ（I））, R（all data） = 0.0413, wR（all data） = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290（3）, b = 20.388（5）, c = 24.092（6） A, β = 102.028（4）°, V = 5424（2） A^3, Z = 4, D_c = 1.428 Mg/cm^（-3）, μ = 1.016 mm^（-1）, F（000） = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections（I 〉 2σ（I））, R（all data） = 0.0716, wR（all data） = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu（I） complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.

Synthesis, Crystal Structures, Thermal Analysis and Magnetic Property of Mono- and Bi-nuclear 1,1-Cyclobutanedicarboxylate Copper Complexes

Two new copper complexes, [Cu（cbdc）（phen）（H2O）]·2H2O （1） and [Cu2（cbdc）（phen）2（H2O）2]（ClO4）2·H2O （2） （cbdc= 1,1-cyclobutanedicarboxylate and phen= 1,10-phenanthroline）, were synthesized by reaction of cbdc with Cu（ClO4）2 and phen in ethanol aqueous solution. Complex 1 crystallizes in monoclinic system with space group P2（1）/c and a=0.9428（4） nm, b= 1.2183（5） nm, c= 1.6265（7） nm, β= 102.418（5）°, V= 1.8246（13） nm^3, Z=4, R=0.0445, wR2=0.0947. The structure of 1 is discretely mononuclear, which is packed by π…π interaction forming a 3D supramolecular structure where Cu（Ⅱ） ion is five-coordinated and has square-pyramidal coordination geometry. Its thermal decomposition procedure detail was studied by thermal analysis TG-DSC. Complex 2 belongs to monoclinic system with space group P2（1）/c and a=0.8897（3） nm, b= 1.9130（8） nm, c= 1.9936（8） nm,β=99.04（2）°, V=3.351（2） nm^3, Z=4, R=0.0540, wR2=0.1102. The structure of 2 is a discrete binucleus, where Cu（1） is four-coordinated by phen and cbdc in a square-planar geometry while Cu（2） is five-coordinated by phen, one O of cbdc and two H2O, which can be best described as distorted trigonal-bipyramidal geometry. Cu（1） and Cu（2） are linked by carboxylic group of cbdc in a bidentate bridging fashion. Variable-temperatttre magnetic susceptibilities of 2 in 2-300 K showed that its magnetic behavior obeyed Curie law.

Synthesis and Crystal Structure of Two One-dimensional Chain Copper Complexes [Cu(TTA)_2(4,4′-azpy)] and [Cu(TTA)_2(3,3′-azpy)]

Two copper complexes [Cu(TTA)(2)(4, 4'-azpy)] (1) and [ Cu- (TTA)(2)(3,3'-azpy)] (2) (HTTA = 1,1,1-trifluoro-3-(2-thenoyl)-acetone, 4,4'-azpy = 4,4'-azobispyridine, 3,3'-azpy = 3,3'-azobispyridine) were synthesized and characterized. The crystal structures were determined by X-ray diffraction analysis. The crystal I belongs to triclinic with space group P1, a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, alpha = 66.126(9)degrees, beta = 79.667(9)degrees, gamma = 90.13(1)degrees, Z = 1, V = 0.6692(2) nm, D-c = 3.425 g/cm(3), mu = 2.113 mm(-1), F(000) = 694, R-1 = 0.0594, wR(2) = 0.1499. The crystal 2 belongs to monoclinic with space group P2(1)/c, a = 1.0661(2) nm, b = 1.4296(3) nm, c = 1.0041(3) nm, beta = 114.50(3)degrees, V = 1.3926(5) nm(3), Z = 2, D-c = 1.646 g/ cm(3), mu = 1.015 mm(-1), F (000) = 694, R-1 = 0.0535, wR(2) = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one-dimensional linear chains linked through the rod- like 4,4'-azpy ligands or 3,3'-azpy ligands.

Supramolecular Formation via Hydrogen Bonding in Copper and Nickel Complexes with 2-Hydroxynicotinic Acid

Two complexes, Cu（HnicO）2 1 and Ni（HnicO）2（H2O）2 2 （H2nicO = 2-hydroxynicolinic acid）, were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in monoclinic, space group P21/n, with a = 8.314（7）, b = 6.275（4）, c = 11.283（7）A, β = 98.32（3）°, V = 582.5（7）A^3, Z = 2, Mr = 339.74, Dc = 1.937 g/cm3, F（000） = 342, μ = 1.908 mm^-1, S = 1.097, the final R = 0.0284 mad wR = 0.0781 for 1177 observed reflections with Ⅰ 〉 2σ（Ⅰ）. Complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.438（5）, b = 12.22（1）, c = 7.537（5）A,β = 100.07（3）°, V= 674.3（8）A3, Z = 2, Mr = 370.95, Dc = 1.827 g/cm^3, F（000） = 380, = 1.487 mm^-1, S = 1.041, the final R = 0.0335 and wR = 0.0779 for 1202 observed reflections with I 〉 2σ（Ⅰ）. There are extended 3D framework structures in complexes 1 and 2 due to the N-H…O and C-H…O hydrogen bonds. The copper atom in 1 has square planar coordination, while the nickel atom in 2 adopts octahedral coordination geometry. The TG curve shows that complex 2 is stable in solid state to 150 ℃.

DNA Cleavage of the Copper(II) Complexes with a Polyamine Ditopic Ligand

A new binuclear complex [Cu2L(OH)](ClO4)3·2H2O has been synthesized and characterized, where L=2,6-bis{[bis-(2-aminoethyl)amino]methyl}-benzene. In the presence of 0.5 mmol/L complex at pH 8.10 and 37°C, the complex can efficiently cleavage pBR322 DNA with a rate constant kobs of 1.35×10-4 s-1. The cleavage occurred by a non-oxidative mechanism showing activity to be dependent on pH.

Synthesis,Structure and Luminescent Properties of Polymeric Copper(Ⅰ) Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.

DNA Cleavage by Copper (Ⅱ) Complexes Without added Coreactants

The cleavage activity of complexes between copper (Ⅱ) and four different amino acidor amino acid methyl ester on DNA was tested at physioloical pH and temperature., It was found that Cu (Ⅱ)-L-His and Cu (Ⅱ)-L-His methyl ester complexes could cleane DNA. The extent ofDNA cleavage is largely dependent on the metal ion-to-ligand ratio. The cleavage of doublestranded DNA mediated by Cu (Ⅱ)-L-His complexes occurs via a hydrolytie mechanism.

Synthesis and Characterization of Dipeptide Schiff Base Complexes of Copper(Ⅱ), Zinc(Ⅱ), Nickel(Ⅱ) and Cobalt(Ⅱ)

A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental analyses, molar conductance, 1H NMR DTA, TG, IR and UV spectroscopy. In these complexes the ligand is coordinated to the metal through its phenolic oxygen, carboxyl oxygen, imino nitrogen and amide nitrogen. All complexes are non-electrolytes and four coordinated with 1:1(metal; ligand) stoichiometry. The probable structure of the complexes is suggested

Synthesis and Magnetic Properties of Copper (Ⅱ) Complexes with Pyridine N-Oxide-2-ylmethy-lidenedithiocarbazate as Ligands

A series of copper (Ⅱ) complexes with pyridine N- oxide- 2- ylmethylidened-ithiocarbazates as ligands were synthesized and characterized by IR spectra, electronic spectra and magnetic moments measurement at room temperature. Variable temperature magnetic susceptibilites (3-300K) of four complexs were measured and fitted with the Bleaney-Bowers dimer equation by considering the magnetic interaction between molecules. The fitting results show the existence of intramolecular ferromagnetic interactions and intermolecu-lar anti-ferromagnetic interactions in these copper( Ⅱ) complexes.