One-step synthesis of carbon-supported copper nanoparticles from biomass for N-arylation of pyrazole

Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and were identified to be Cu（0） and Cu（Ⅰ） in XRD patterns. Excellent catalytic activity and selectivity were achieved in the N-arylation of pyrazole under ligand and protection gas free conditions. About90.4% of product yield was achieved with only 0.5 mol% of copper catalyst（Cu-C-300）, which was considerably more efficient than previous reports. XPS results suggested that the N-arylation of pyrazole activity was closely related to the surface Cu（Ⅰ） species.

A Copper(Ⅱ)Complex Based on N-(4-hydroxybenzyl)-L-serine:Synthesis,Crystal Structure and Inhibitory Activity on PTP1B and TCPTP

A novel copper（II） complex with the reduced Schiff base, [Cu（L）2]·H2O （I, HL = N-（4-hydroxybenzyl）-L-serine）, was prepared in aqueous solution and characterized by elemental analysis, FT-IR, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a = 8.9040（18）, b = 9.1530（18）, c = 24.891（5）A^°, V = 2028.6（7） A^°3, Z = 4, C20H26CuN2O9, Mr = 501.97, Dc = 1.644g·cm^3, μ = 1.135 mm^-1, F（000） = 1044, GOOF = 1.194, the final R = 0.0484 and wR = 0.1420 for 6186 observed reflections （I 〉 2σ（I））. In I, two L^- anions are coordinated to the copper ion in tridentate and bidentate chelating modes, respectively, resulting in the coordinated geometry of copper ion to be a distorted square pyramid. The intermolecular hydrogen bonds between the complexes, complexes and lattice water molecules lead to a 2D supramolecular network. The bioactivity of the complex as a potential PTPs inhibitory agent in vitro was investigated, displaying potent inhibition against PTP1B （IC50, 0.27 μM） and TCPTP （IC50, 0.57 μM） with a moderate selectivity.

Synthesis and Structure of bis(μ-2-aminopyridine N-oxide)-bis[dichlorocopper(II)]

The complex [Cu2（apo）4Cl4]·2H2O （apo=2-aminopyridine N-oxide） was obtained. A single- crystal X-ray study shows that the complex is a binuclear compound （Cu2C20H28Cl4N8O6）. The coordination geometry about each copper atom is best described as a distorted square pyramid. The compound [Cu2（apo）4Cl4]·2H2O belongs to the triclinic system with space group P, lattice constants: a = 7.8550（7）, b = 8.5378（7）, c = 12.082（1） ?, α = 72.807（1）, β = 77.641（1）, γ = 70.800（1）(, V =724.85（11） ?3, Z=1, Mr =745.38, Dc=1.708 g/cm3, μ =1.886mm-1, F（000） =378, R=0.0359, wR2=0.0884 for 2220 reflections with I >2σ（I）. The distances between Cu（II） and O atoms are in the range from 1.934（2） to 2.042（2）?. The distance between two copper atoms Cu-Cu（A） is 3.2978（8） ?. The distances of Cu-Cl（1） and Cu-Cl（2） are 2.2322（9）, 2.5095（10） ?, respectively. There is no evident hydrogen bond between N and Cl.

Microwave-assisted chemoselective copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aromatic amines under solvent free conditions

Copper-catalyzed synthesis of N-aryl anthranilic acid derivatives using effective amination of 2-chloro and 2-bromobenzoic acid under microwave irradiation is reported. Some of the advantages of this method are high chemoselectivity, short reaction times, ease of work up procedure and elimination of the need for acid protection. 2009 Published by Elsevier B.V. on behalf of Chinese Chemical Society.

Synthesis and Characterization of Free and Copper (II) Complex of N,N′-<i>Bis</i>(Salicylidene)Ethylenediamine for Application in Dye Sensitized Solar Cells

Dye sensitized solar cell represents a promising method for the conversion of solar energy to electric energy. In the present work free N,N'-bis(salicyli-dene)ethylenediamine and its copper (II) complex were synthesized, characterized, and investigated for use as dye sensitizers in the fabrication of dye sensitized solar cells. The dyes were characterized using UV-Vis, Steady State Florescence, and Fluorescence Lifetime, Thermogravimetric Analysis, Differential Scanning Calorimetry, and Cyclic Voltammetry. The thermogravimetric analyses of the ligand and the ligand Copper complex demonstrate the stabilizing effect of the copper ion on the ligand complex. Additionally, the copper ion is shown to stabilize the structure, as evidenced by the 150oC increase in the extrapolated onset temperature of the decomposition event. The ligand copper complex is further stabilized by the presence of the copper, which is determined by the 6.34% residue that remained at the end of the thermogravimetric analysis, compared with 0% residue when applying the same condition for the ligand without copper. The current-voltage characteristics of the cells and the electrochemical impedance were determined. The photovoltaic performance of the solar cell devices fabricated using N,N'-bis(salicylidene) ethylenediamine dye was found to be slightly better than those produced from the copper complex. The solar to electric power efficiency of the ligand-based dye sensitized solar cell was 0.14% and that of the copper complex was found to 0.12%. Although the difference in the cell efficiency is quite small, it is obvious that the insertion of Copper into the ligand did not enhance the performance of the solar cells. The photocurrent-photovoltage results are consistent with the absorption spectra that showed a more prominent band for the ligand. The free hydroxyl groups, present in the ligand but absent from the copper complex owing to their coordination with the copper metal, could be responsible for the difference in the performance of the devices. The hydroxyl groups get attached to the TiO2 and facilitate the transfer of electrons.

Synthesis and Crystal Structure of a Copper(Ⅱ) Compound Constructed by N-(4,6-Dimethoxylpyrimidin)-N'-(ethoxycarbonyl)thiourea

A copper（Ⅱ） complex Cu（L）2（NO3）2 constructed by the L （L = N-（4,6-dimethoxylpyrimidin）-N＇-（ethoxycarbonyl）thiourea） ligand crystallizes in monoclinic, space group C2/c with a = 16.2416（16）, b = 9.1385（7）, c = 22.0008（18） A, β = 108.077（2）°, V = 3104.3（5） A^3, Dc = 1.627 g/cm^3, Z = 4, C20H28CuN10O14S2, Mr = 760.18,μ（MoKa） = 0.920 mm^-1, F（000） = 1564, R = 0.0471 and wR = 0.1284 for 2239 observed reflections （I 〉 2σ（I））. X-ray diffraction shows the existence of weak complementary intramolecular N-H...O （DA） hydrogen bonds which further strengthen the coordination from the two L ligands with the Cu（Ⅱ） ion, intermolecular C-H...O hydrogen bonds and weak π...π stacking interactions, leading to the formation of a multi-dimensional supramolecular network.

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.

A Diphenoxo-bridged Ferromagnetic Copper(Ⅱ) Dimer Based on N-(2-Hydroxybenzyl)salicylaldimine

A new dinuclear copper（Ⅱ） complex, [Cu（L）（py）]2 1 （H2L = N-（2-hydroxybenzyl）- salicylaldimine, py = pyridine）, has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ（MoKα） = 1.422 mm-1, F（000） = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper（H） centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper（Ⅱ） ion and shares the other phenolate group between the two copper（H） ions, affording a Cu2O2 plane. Each copper（Ⅱ） center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data （2-300 K） of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑（Xobsd -Xcalcd）2/∑Xobsd2= 2.76 × 10^-3.

Synthesis,Crystal Structure and Antimicrobial Study of N,N,N'-Tris(3-aminopropyl)ethylenediamine Copper(Ⅱ) Diperchlorate

The title compound [Cu（C11H29N5）]（ClO4）2 was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system, space group P21/n with α = 9.405（2）, b = 14.495（3）, c = 14.715（3） A, β= 90.262（3）°, V=2006.1（7） A^3,M,=493.83,Z=4,F）（000）= 1028,Dc= 1.635 g/cm^3, T= 298（2） K,μ= 1.403 mm^-1 and = 0.71073 A. The was refined to R = 0.0508 and wR = 0. 1250 for 2293 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom possesses a five-coordtinate CuN5 environment which shows a slightly distorted square-pyramidal geonetry. Antimicrobial activity study found that the complex is active against Salmonella species, Staphylococcus aureu, Bacillus pumilus and Bacillus coliforms.

一种NHC-Cu(Ⅱ)配合物的合成及其对乙苯的催化氧化反应研究

以苯并咪唑为原料合成氮杂卡宾(NHC)前体1,3-双(2-羟基-3,5-二叔丁基苄基)苯并咪唑氯化物,再与CuCl 2配位制备NHC-Cu(Ⅱ)配合物,分别采用紫外-可见吸收光谱、红外光谱、X射线电子能谱和质谱对该配合物进行了结构表征.将该配合物(1%(mol))作为催化剂,以叔丁基过氧化氢(TBHP)为氧化剂,在353 K的乙腈溶液中对乙苯以及其衍生物进行催化氧化反应,结果表明,乙苯的α-H被选择性氧化,首先生成苯乙醇,而后被继续氧化为苯乙酮,乙苯在反应12 h后的转化率为68%,苯乙酮的选择性为90%,苯环上连有吸电子基时,催化氧化效果更佳.

Copper-mediated synthesis of N,N'-diarylhydrazines from boronic acids

N,N＇-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.

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.

Synthesis and Structure of a New Copper(II) Complex Cu(C_(13)H_9N_3O_2Br)_2.H_2O

The new copper(II) complex Cu(C13H9N3O2Br)2H2O (N-(2-hydroxy-5-bromo- benzoyl)-N-(picolinylidene)hydrazine is abbreviated as HL ) was obtained from the refluxing solution of Cu(CH3COO)2H2O and HL in the ethanol-N, N-dimethylformamide mix solvent. Crystal data: triclinic, space group P , a = 10.8620(3), b = 11.7453 (3), c = 12.4417(2) ? ?= 62.255(0), ?= 79.097(2), ?= 86.764(2)? V = 1378.52(6) ?, Z = 2, Mr = 719.835, Dc = 1.734 g/cm3, F(000) = 714, (MoK) = 3.739 mm-1, T = 293(2) K, final R = 0.0594 and wR = 0.1416 for 2943 observed reflections with I > 2.0(I). The structure of Cu(C13H9N3O2Br)2H2O has been determined by X-ray analysis and revealed that two L-1 ligands coordinate to the copper(Ⅱ) ion through two oxygen and two nitrogen atoms from the hydrazine groups and two pyridine nitrogen atoms to form an elongated and distorted square-bipyramidal environment for Cu(Ⅱ). The complex is also characterized by 1H NMR

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

6-(N,N-Dimethylamino)-2-naphthoylacryl Acid:a Highly Selective and Sensitive Fluorescent Sensor of Copper(Ⅱ)

A novel fluorescent probe,6-（N,N-dimethylamino）-2-naphthoylacryl acid（ACADAN） was designed and synthesized as a fluorescent sensor for Cu^2＋ in aqueous media.Significant amplification of fluorescence signals without causing any discernible change of maximum fluorescence emission wavelength（λ max） was observed upon the addition of Cu^2＋.Importantly,ACADAN is capable of recognizing Cu^2＋ selectively in aqueous media in the presence of various biologically relevant metal ions and the prevalent toxic metal ions in the environment with high sensitivity（detection limit was 0.1 μmol/L）.

Synthesis and Crystal Structure of a Novel Polymer Copper(Ⅱ) Complex

A novel chain complex was synthesized and its crystal structure has been deter- mined by X-ray diffraction technique. It was found that the local coordination geometry around Cu(Ⅱ) is a distorted tetrahedron and C14H9CuNO3CH3OH is bridged by the carboxylate oxygen atom to form an infinite one-dimensional linear chain. The hydrogen bond exists between O(1) and solvate molecule O(4). The crystal belongs to monoclinic, space group P21 with a = 9.6650(19), b = 7.1280(14), c = 9.925(2) ? b = 98.39(3)? V = 676.4(2) 3, Z = 2, F(000) = 342 and m(MoK? = 1.629 mm-1 .

不同N水平下缘管浒苔对重金属铜的响应

探讨了重金属铜对两种N水平生长条件下缘管浒苔生长、光合作用、硝酸还原酶活性以及色素和蛋白含量的影响。结果表明,两种N水平下,铜离子都显著抑制藻体的生长速率,并且随着浓度的增加而增大;而N加富显著促进藻体的生长速率,但这种作用在高浓度铜(2μM)的作用下不显著。高浓度的铜和N同时存在时,藻体的光合作用速率显著下降,硝酸还原酶活性也显著降低。高浓度的铜显著降低类胡萝卜素和可溶性蛋白的含量,在N加富的情况下,这种抑制作用更为显著。

N-甲基咪唑与2,2’-联吡啶在铜表面共吸附的SERS研究

采用电化学现场表面增强拉曼光谱(SERS)分别研究了非水体系中N-甲基咪唑(NMIM),2,2’-联吡啶(2,2-’bipy)在铜电极表面的吸附行为以及两者的共吸附行为。结果表明在非水体系中,NMIM可在很宽的电位区间内稳定地吸附在金属表面,而2,2-’bipy在一个相对较窄的电位区间内能稳定地吸附在金属表面。当两者共存时存在竞争吸附和共吸附行为,较负的电位下主要以NMIM吸附为主,在略偏负的电位区间内以2,2-’bipy吸附为主,而正电位区间两者在金属表面共吸附,NMIM倾斜吸附在金属表面,而2,2’-bipy以顺式结构垂直吸附在金属表面。

蒙脱土负载Cu^＋催化含氮杂环化合物的N-芳基化反应(英文)

通过简单的离子交换法制备出蒙脱土(MMT)负载Cu+催化剂,采用X射线衍射,X射线光电子能谱,扫描电子显微镜和X射线能量色散谱等技术对催化剂样品进行了表征.结果表明,Cu+已经成功的插入到蒙脱土层间.在芳基氯或芳基溴与含氮杂环化合物的N-芳基化反应中,催化剂显示出高的催化活性,且可通过简单的过滤分离出该催化剂,重复使用4次其活性无明显降低.