Copper(I)-Catalyzed Aryl Bromides To Form Intermolecular and Intramolecular Carbon-Oxygen Bonds

A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K3PO4 as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

One-pot synthesis and self-assembly of colloidal copper(I) sulfide nanocrystals

A simple one-pot method is developed to prepare size-and shape-controlled copper(I) sulfide (Cu2S) nanocrystals by thermolysis of a mixed solution of copper acetylacetonate, dodecanethiol and oleylamine at a relatively high temperature. The crystal structure, chemical composition and morphology of the as-obtained products are characterized by powder x-ray diffraction (PXRD), x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The morphology and size of the Cu2S nanocrystals can be easily controlled by adjusting the reaction parameters. The Cu2S nanocrystals evolve from spherical to disk-like with increasing reaction temperature. The spherical Cu2S nanocrystals have a high tendency to self-assemble into close-packed superlattice structures. The shape of the Cu2S nanodisks changes from cylinder to hexagonal prism with prolonged reaction time, accompanied by the diameter and thickness increasing. More interestingly, the nanodisks are inclined to self-assemble into face-to-face stacking chains with different lengths and orientations. This one-pot approach may extend to synthesis of other metal sulfide nanocrystals with different shapes and sizes.

An Efficient Ullmann-Type C-O Bond Formation Catalyzed by an Air-Stable Copper(I)-Bipyridyl Complex

An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.

Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing beta-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L-1)PPh3 (1), Cu(L-2)(PPh3)(2) (2) ([L-1](-) = [{N((C6H3Pr2)-Pr-i-2,6)C(H)}(2)CPh](-); [L-2](-) = [{N(C6H5)C(H)}(2)CPh](-)) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered beta-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.

Novel luminescent iminephosphine complex of copper(I) with high photochemical and electrochemical stability

Luminescent heteroleptic Cu-I complexes based on asymmetrical iminephosphine ligands exhibit improved electrochemical and photochemical stability as compared to the analogous complexes based on traditional diimine or diphosphine ligands.

咪唑衍生物为配体的铜(I)配合物合成及光物理性质

本论文以咪唑衍生物为配体,合成了新型Cu(I)中性配合物和对应的离子型配合物，考察了它们的光物理和电化学性质。具体工作如下： 设计与合成了分别以2-(2'-吡啶基)苯并咪唑(Hpbm)和2-(2'-喹啉基)苯并咪唑(Hqbm)为配体的Cu(I)中性配合物和四氟硼酸根为抗衡离子的离子型配合物。配合物的晶体结构表明中心铜离子均为扭曲的四面体配位构型，中性配合物的咪唑环中的键长趋于平均化。所有配合物在20wt%浓度的PMMA薄膜中的最大发射处于518.5-597.5nm之间，发光效率为0.097-0.249, 磷光寿命为11.7-25.9µs。中性配合物与对应的离子型配合物相比，其紫外可见吸收光谱发生红移，光致发光光谱发生蓝移。 以2, 2'-联苯并咪唑为配体(H2dbm)，设计和合成了双核和单核Cu(I)配合物，其中双核配合物Cu2(dbm)(PPh3)4在二氯甲烷溶液和PMMA (20 wt%)薄膜中均表现为蓝光发射，在20wt%浓度的PMMA薄膜中的最大发射为448.5和475.5nm。单核离子型配合物[Cu(Hdbm)(PPh3)]2[BF4]在20wt%浓度的PMMA薄膜中的最大发射分别为511，发光效率分别为0.150, 磷光寿命分别为12.0。

Preparation and gas sensitivity of octa-n-butoxy-2,3-naphthalocyanine copper(II) Langmuir-Blodgett film

The formation process of monolayer of octa-n-butoxy-2,3-naphthalocyanine copper ( I), [CuNc(OBu)(8)], on water subphase was studied. Its multilayers were successifully deposited on the hydrophilic substrates by Z-type deposition mode using LB technique. Stable solid film with a limiting molecular area of 0.74 nm(2) and a collapse pressure of 55 mN/m were formed. The LB film structure was characterized by IR and electronic absorption spectra. Macrocycle of CuNc (OBu)(8) molecules have a face-to-face arrangement in the multilayers. These films have good sensitivities to vapor of alcohols, with the following sequence of sensitivities: i-PrOH>EtOH>MeOH. The response time and recovery time of the LB films to vapor of MeOH, EtOH and i-PrOH[volume fraction (1-5) X 10(-5)] were within 2 and 5 seconds respectively, while those of the LB films to ammonia(1 X 10(-4)) were 30-60 seconds and 4-5 minutes respectively.

The oxidative demethylation of 24-membered hexa-aza macrocyclic bicopper(I) complex - The mimicking for monooxygenase

By [2 + 2] Schiff base condensation of 5 - bromo - 2 - methoxylbenzene - 1,3 - dicarboxaldehyde with diethylenetriamine, a new hexaaza 24 - membered macrocyclic ligand was obtained,which formed a macrocyclic binuclear copper(I) complex in the presence of [Cu . (CH3CN)(4)]ClO4. When the copper(I) complex was oxidized in air or oxygen, a new macrocyclic binuclear copper( II) complex was obtained. The copper( II.) complex was characterized by several methods and its oxidized products was characterized by H-1 NMR. The results show that during oxidation, a methoxyl group in the ligand ring broke; and the phenoxy - and water - bridged Cu(II) complex formed. In oxidation of monooxygenase such as ligninase, oxidative demethylation also happened. Therefore this work mimicked this process for the first time by using macrocyclic complex. The quantity of absorbed oxygen and the absorption rate of oxygen were determined.

一价铜催化Ullmann 反应合成联苯醚和芳基烷基醚的研究

联苯醚和芳基烷基醚类化合物是天然产物和聚合物材料中的重要的片段结构，研究其合成具有重要意义。近年来，过渡金属催化形成碳-氧键已成为制备联苯醚和芳基烷基醚类化合物的重要方法。钯体系虽然成功，但由于其属于贵金属，价格昂贵，而且反应所必须的有机膦配体，毒性较大，对环境危害较大，所以其应用受到了限制。 本论文通过利用空气稳定的Cu(bpy)2BF4 配合物，使得苯酚和烷基醇有效地进行偶合得到联苯醚产物。该方法可以在不使用昂贵弱碱Cs2CO3 的情况下，取得很好的产率，并且在较低的催化剂载入量的情况下，可以很好地适应各种官能团取代的底物。 本论文通过配体的扫描筛选，使得溴代苯和烷基醇的偶合反应得到了发展。更重要的是，使用该体系时分子间和分子内的碳-氧键都可以形成。通过该方法合成了一系列苯并环醚类化合物，这也是一价铜体系催化制备该类化合物的首次报道。

Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to Alkynes

The B3LYP hybrid density functional method has been carried Out to Study theoretically the mechanisin of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH3)(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH3)2, and in path C of each reaction, the first step is the PH3 dissociation front Pd(PH3)2 to form monophosphine complex Pd(PH3) For both reactions, path B is favored.

Theoretical Studies on the Reaction Mechanism of Platinum-Catalyzed Diboration of Allenes

The reaction mechanism of Pt(0)-catalyzed diboration reaction of allenes is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. The electronic mechanisms of the allene insertion into the Pt-B bond are discussed in terms of the electron donation, back-donation, and d-pi interaction. During allene insertion into the Pt-B bond, the internal carbon atom of allene is preferred over the terminal one due to the stronger electron back-donation and stronger charge transfer in the former case than that in the latter one.

Reaction Mechanism of Palladium-Catalyzed Silastannation of Allenes by Density Functional Theory

The reaction mechanism of Pd(O)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed ill terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.

Molecular dynamics simulation of plastic deformation of nanotwinned copper

The plastic deformation of polycrystalline Cu with ultrathin lamella twins has been studied using molecular dynamics simulations. The results of uniaxial tensile deformation simulation show that the abundance of twin boundaries provides obstacles to dislocation motion, which in consequence leads to a high strain hardening rate in the nanotwinned Cu. We also show that the twin lamellar spacing plays a vital role in controlling the strengthening effects, i.e., the thinner the thickness of the twin lamella, the harder the material. Additionally, twin boundaries can act as dislocation nucleation sites as they gradually lose coherency at large strain. These results indicate that controlled introduction of nanosized twins into metals can be an effective way of improving strength without suppression tensile ductility. (C) 2007 American Institute of Physics.

Optical parameters and absorption of copper (II)-azo complexes thin films as optical recording media

Smooth thin films of three kinds of azo dyes of 2-(5'-tert-butyl-3'-azoxylisoxazole)-1, 3-diketones and their copper (II)-azo complexes were prepared by the spin-coating method. Absorption spectra of the thin films on a glass substrate in the 300-600 nm wavelength region were measured. Optical constants (complex refractive index N=n+ik) and thickness of the thin films prepared on single-crystal silicon substrate in the 300-600 nm wavelength region were investigated on rotating analyzer-polarizer type of scanning ellipsometer, and dielectric constants epsilon(epsilon=epsilon(1)+i epsilon(2)), absorption coefficients alpha as well as reflectance R of thin films were then calculated. In addition, one of the copper (II)-azo complex thin film prepared on glass substrate with an Ag reflective layer was also studied by atomic force microscopy (AFM) and static optical recording. AFM study shows that the copper (II)-azo complex thin film is very smooth and has a root mean square surface roughness of 1.89 nm. Static optical recording shows that the recording marks on the copper (II)-azo complex thin film are very clear and circular, and the size of the minimal recording marks can reach 200 nm. (c) 2004 Elsevier B.V. All rights reserved.

Pool boiling heat transfer of ultra-light copper foam with open cells

High speed visualizations and thermal performance studies of pool boiling heat transfer on copper foam covers were performed at atmospheric pressure, with the heating surface area of 12.0 mm by 12.0 mm, using acetone as the working fluid. The foam covers have ppi (pores per inch) from 30 to 90, cover thickness from 2.0 to 5.0 mm, and porosity of 0.88 and 0.95. The surface superheats are from -20 to 190 K, and the heat fluxes reach 140 W/cm(2). The 30 and 60 ppi foam covers show the periodic single bubble generation and departure pattern at low surface superheats. With continuous increases in surface superheats, they show the periodic bubble coalescence and/or re-coalescence pattern. Cage bubbles were observed to be those with liquid filled inside and vented to the pool liquid. For the 90 ppi foam covers, the bubble coalescence takes place at low surface superheats. At moderate or large surface superheats, vapor fragments continuously escape to the pool liquid. Boiling curves of copper foams show three distinct regions. Region I and II are those of natural convection heat transfer, and nucleate boiling heat transfer for all the foam covers. Region III is that of either a resistance to vapor release for the 30 and 60 ppi foam covers, or a capillary-assist liquid flow towards foam cells for the 90 ppi foam covers. The value of ppi has an important effect on the thermal performance. Boiling curves are crossed between the high and low ppi foam covers. Low ppi foams have better thermal performance at low surface superheats, but high ppi foams have better one at moderate or large surface superheats and extend the operation range of surface superheats. The effects of other factors such as pool liquid temperature, foam cover thickness on the thermal performance are also discussed.