We developed a modified protocol for the oxidation of 2,3-allenyl alcohols using CuCI with l ： 1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, ...We developed a modified protocol for the oxidation of 2,3-allenyl alcohols using CuCI with l ： 1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested： we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.展开更多
The authors made the electrochemical studies on the electrode processes during copper electrodeposition with ionic liquids-reline as an electrolytic medium. Reline is a commercial name for a eutectic mixture of cholin...The authors made the electrochemical studies on the electrode processes during copper electrodeposition with ionic liquids-reline as an electrolytic medium. Reline is a commercial name for a eutectic mixture of choline chloride and urea（1：2, molar ratio）. This new proposed method of copper deposition is an ecological one because the ionic liquids are recyclable, non-volatile and non-toxic. Cyclic voltammetry investigations were conducted at 343 and 353 K in choline chloride-urea（Reline） deep eutectic solvent with single salt CuCl（generally in 0.05--0.38 mol/L concentration range）. Electrochemical impedance spectroscopy investigations were conducted in choline chloride- urea ionic liquid with CuCI（0.05 mol/L）. We investigated both cathodic and anodic processes of Cu＋ ions at different sweep rates in this new electrolytic system based on choline chloride. We have proposed by this an alternative to the classical copper electrodeposition. Coefficient of diffusion, Do, for the system Reline-CuCl is presented and the value of D0 is 1.22× 10^-8 cm2/s.展开更多
A new emissive mononuclear homoleptic Cu（Ⅰ） complex of 5-rert-butyl-3-（6-methyl-2-pyridyl）-1H-1,2,4-triazole（bmptzH）,[Cu（bmptzH）2]（ClO4）（1）,has been synthesized by treatment of[Cu（PPh_3）2（CH3CN）2]（C...A new emissive mononuclear homoleptic Cu（Ⅰ） complex of 5-rert-butyl-3-（6-methyl-2-pyridyl）-1H-1,2,4-triazole（bmptzH）,[Cu（bmptzH）2]（ClO4）（1）,has been synthesized by treatment of[Cu（PPh_3）2（CH3CN）2]（ClO4） or [Cu（CH3CN）4]（ClO4） with the bmptzH ligand.It is revealed that complex 1 displays a distorted N4 tetrahedral arrangement formed by two bmptzH chelates,in which bmptzH adopts a neutral bidentate chelating coordination mode using the N atom of the pyridyl ring and the 4-N not 2-N atom of the 1,2,4-triazolyl ring.It is shown that complex 1 is highly stable and exhibits good luminescence properties in solution and solid states at room temperature due to the introduction of a methyl group at the ortho-position of the pyridyl ring.展开更多
The title compound {[Cu（abpy）2]（H3bptc）·（H2O）}n, an ion-pair complex of [Cu（abpy）2]＋ with [（H3bptc）]- （abpy = 3,3＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2＇,3,3＇-tetracarboxylic a...The title compound {[Cu（abpy）2]（H3bptc）·（H2O）}n, an ion-pair complex of [Cu（abpy）2]＋ with [（H3bptc）]- （abpy = 3,3＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2＇,3,3＇-tetracarboxylic acid）, has been synthesized by a hydrothermal reaction, and its structure was deter- mined by X-ray diffraction and characterized by elemental analysis and IR spectrum. The crystal is of triclinic, space group P1 with a = 8.4955（12）, b = 15.164（2）, c = 15.303（2）, α = 105.704（3）, β = 97.374（3）, γ = 96.764（3）o, CuC40H35N4O9, Mr = 779.26, V = 1857.9（4）3, Dc = 1.393 g/cm3, F（000） = 808, μ = 0.649 mm-1, S = 1.026 and Z = 2. The final R = 0.0493 and wR = 0.1034 for 4026 observed reflections with I 2σ（I）. The copper（I） coordination polymer demonstrates a 3-D sandwich-type structure containing 2-D double H3bptc-chain layers intercalated with the [Cu（abpy）2]＋ layers by extensive hydrogen bonding interactions.展开更多
The first catalytic enantioselective C（sp）-C（sp^3） cross-coupling reaction between N-tosylhydrazones and trialkylsilylethynes in the presence of Cu（I） salts and chiral phosphoramidite ligands was developed. A se...The first catalytic enantioselective C（sp）-C（sp^3） cross-coupling reaction between N-tosylhydrazones and trialkylsilylethynes in the presence of Cu（I） salts and chiral phosphoramidite ligands was developed. A series of svnthetically interesting, functionalized alkynes were obtained with moderate to good enanttiselectivities （up to 83% ee）. Cu（ll） carbene migratory insertion is proposed to be the enantio-determining step. KEYWORDS C（sp）--C（sp^3） cross-coupling, metal carbene, asymmetric catalysis, Cu（I） catalysts, N-tosylhydrazones展开更多
The present article reports a novel self‐standing nanostructured Au‐Cu(I)@Na2Ti6O13plasmonic photocatalytic membrane,which is prepared by a hydrothermal reaction followed by a simple subsequent heat treatment proces...The present article reports a novel self‐standing nanostructured Au‐Cu(I)@Na2Ti6O13plasmonic photocatalytic membrane,which is prepared by a hydrothermal reaction followed by a simple subsequent heat treatment process.The morphological structure,elemental composition,crystalline phases,and optical properties of the membrane were studied in detail by field‐emission scanning electron microscopy,transmission electron microscopy,X‐ray photoelectron spectroscopy,X‐ray diffraction,and ultraviolet‐visible spectroscopy.Compared with that of a pure Na2Ti6O13membrane,the Au‐Cu(I)@Na2Ti6O13membrane displayed much higher photocatalytic activity for the decomposition of acetaldehyde,a typical volatile organic compound,under visible light illumination.It was found that the photocatalytic activity of the Au‐Cu(I)@Na2Ti6O13membrane increased as the amount of Au was increased.The membrane loaded with2.85wt%Au showed the highest photocatalytic activity in the decomposition of acetaldehyde of the investigated materials.We found that in the photocatalyst membrane,Na2Ti6O13acted as a support material,Au displayed plasmonic absorption,and Cu(I)behaved as a co‐catalyst.The present membrane materials can avoid the self‐aggregation typically observed during the course of photocatalytic reactions.As a result,they can be easily separated,recycled,and reactivated after their practical application,making these functional materials attractive for use in air cleaning applications.展开更多
The click reaction is one of the latest techniques for the functional analysis of bioactive compounds and the analysis makes novel concepts and strategies for medicinal chemistry. N-methylated glycine derivatives have...The click reaction is one of the latest techniques for the functional analysis of bioactive compounds and the analysis makes novel concepts and strategies for medicinal chemistry. N-methylated glycine derivatives have inhibitory activity for the click reaction in direct Cu(I) system because of decrease of Cu(I) concentration. The Cu(I) concentration recovered effectively by sodium ascorbate. Quantitative determination of click reaction at various ligand concentrations revealed that the decrease in reaction yields was observed in a substrate concentration-dependent manner.展开更多
An unusual 3D porous network assembled by tridentate ligand Tbmiz [1,3,5- tris（benzimidazol-1-ylmethyl）-2,4,6-trimethylbenzene] and Cu-I cluster was synthesized by means of hydrothermal process. It crystallizes in t...An unusual 3D porous network assembled by tridentate ligand Tbmiz [1,3,5- tris（benzimidazol-1-ylmethyl）-2,4,6-trimethylbenzene] and Cu-I cluster was synthesized by means of hydrothermal process. It crystallizes in the trigonal system, space group P-3c1 with a = 14.2362（8）, b = 14.2362（8）, c = 36.4017（35）A, γ = 120.00°, V = 6389.1（8）, Dc = 1.976 g/cm^3, Z = 2, μ（MoKα） = 0.71073 and F（000） = 3692.0. Of the 40832 total reflections, 3948 were unique （Rint = 0.0366）. The final R = 0.0460 and wR = 0.1335 for 3948 observed reflections with I 〉 2σ（I）.展开更多
An air-stable supported Cu(I) catalyst, Cu I@PS-Phen, was designed and synthesized. Cu I@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable pol...An air-stable supported Cu(I) catalyst, Cu I@PS-Phen, was designed and synthesized. Cu I@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable polytriazoles with high molecular weights(Mw up to 30800), and low copper residue content(down to 190 ppm) in high yields(up to 94.2%) under mild reaction conditions without the exclusion of oxygen.展开更多
In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(Ⅰ) coordination polymer [CuI(DBBD)_2]_n (2) by inducing a bidentate organic...In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(Ⅰ) coordination polymer [CuI(DBBD)_2]_n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P21, and a=0.881 30(19) nm, b=1.966 0(6) nm, c=1.478 1(4) nm, β=119.429(12)°, V=2.230 5(10) nm3, Dc=1.276 g·cm-3. The crystal 2 belongs to orthogonal system with space group Fmm2, and a=2.044 41(17) nm, b=1.543 06(13) nm, c=1.652 45(13) nm, V=5.212 9(7) nm3, Dc=1.669 g·cm-3, Z=8. CCDC: 292931, 1; 292934, 2.展开更多
文摘We developed a modified protocol for the oxidation of 2,3-allenyl alcohols using CuCI with l ： 1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested： we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.
文摘The authors made the electrochemical studies on the electrode processes during copper electrodeposition with ionic liquids-reline as an electrolytic medium. Reline is a commercial name for a eutectic mixture of choline chloride and urea（1：2, molar ratio）. This new proposed method of copper deposition is an ecological one because the ionic liquids are recyclable, non-volatile and non-toxic. Cyclic voltammetry investigations were conducted at 343 and 353 K in choline chloride-urea（Reline） deep eutectic solvent with single salt CuCl（generally in 0.05--0.38 mol/L concentration range）. Electrochemical impedance spectroscopy investigations were conducted in choline chloride- urea ionic liquid with CuCI（0.05 mol/L）. We investigated both cathodic and anodic processes of Cu＋ ions at different sweep rates in this new electrolytic system based on choline chloride. We have proposed by this an alternative to the classical copper electrodeposition. Coefficient of diffusion, Do, for the system Reline-CuCl is presented and the value of D0 is 1.22× 10^-8 cm2/s.
基金supported by the National Natural Science Foundation of China(Nos.21561013,21501077)the Major Program of Jiangxi Provincial Natural Science Foundation of China for Young Scholar(Nos.20143ACB21017,20161ACB21013)+1 种基金the Jiangxi Provincial Natural Science Foundation of China(Nos.20142BAB203001,20151BAB213003)the Program for Qingjiang Excellent Young Talents of Jiangxi University of Science and Technology
文摘A new emissive mononuclear homoleptic Cu（Ⅰ） complex of 5-rert-butyl-3-（6-methyl-2-pyridyl）-1H-1,2,4-triazole（bmptzH）,[Cu（bmptzH）2]（ClO4）（1）,has been synthesized by treatment of[Cu（PPh_3）2（CH3CN）2]（ClO4） or [Cu（CH3CN）4]（ClO4） with the bmptzH ligand.It is revealed that complex 1 displays a distorted N4 tetrahedral arrangement formed by two bmptzH chelates,in which bmptzH adopts a neutral bidentate chelating coordination mode using the N atom of the pyridyl ring and the 4-N not 2-N atom of the 1,2,4-triazolyl ring.It is shown that complex 1 is highly stable and exhibits good luminescence properties in solution and solid states at room temperature due to the introduction of a methyl group at the ortho-position of the pyridyl ring.
基金supported by the National Natural Science Foundation of China (No. 10947162)the Natural Science Foundation of Henan Province (No. 2010A140009)the International Technology Cooperation Project of Science and Technology Department of Henan Province (No. 104300510044)
文摘The title compound {[Cu（abpy）2]（H3bptc）·（H2O）}n, an ion-pair complex of [Cu（abpy）2]＋ with [（H3bptc）]- （abpy = 3,3＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2＇,3,3＇-tetracarboxylic acid）, has been synthesized by a hydrothermal reaction, and its structure was deter- mined by X-ray diffraction and characterized by elemental analysis and IR spectrum. The crystal is of triclinic, space group P1 with a = 8.4955（12）, b = 15.164（2）, c = 15.303（2）, α = 105.704（3）, β = 97.374（3）, γ = 96.764（3）o, CuC40H35N4O9, Mr = 779.26, V = 1857.9（4）3, Dc = 1.393 g/cm3, F（000） = 808, μ = 0.649 mm-1, S = 1.026 and Z = 2. The final R = 0.0493 and wR = 0.1034 for 4026 observed reflections with I 2σ（I）. The copper（I） coordination polymer demonstrates a 3-D sandwich-type structure containing 2-D double H3bptc-chain layers intercalated with the [Cu（abpy）2]＋ layers by extensive hydrogen bonding interactions.
基金Acknowledgement The project is supported by the National Basic Research Program of China （973 Program, No. 2015CB856600）, the National Natural Science Foundation of China （Grant 21472004, 21332002） and the China Postdoctoral Science Foundation Funded Project （2015M5B0911）.
文摘The first catalytic enantioselective C（sp）-C（sp^3） cross-coupling reaction between N-tosylhydrazones and trialkylsilylethynes in the presence of Cu（I） salts and chiral phosphoramidite ligands was developed. A series of svnthetically interesting, functionalized alkynes were obtained with moderate to good enanttiselectivities （up to 83% ee）. Cu（ll） carbene migratory insertion is proposed to be the enantio-determining step. KEYWORDS C（sp）--C（sp^3） cross-coupling, metal carbene, asymmetric catalysis, Cu（I） catalysts, N-tosylhydrazones
基金supported by the National Natural Science Foundation of China(51772230,51461135004)Hubei Foreign Science and Technology Cooperation Project(2017AHB059)the Japan Society for the Promotion of Science(JSPS)for an Invitation Fellowship for Foreign Researchers(L16531)~~
文摘The present article reports a novel self‐standing nanostructured Au‐Cu(I)@Na2Ti6O13plasmonic photocatalytic membrane,which is prepared by a hydrothermal reaction followed by a simple subsequent heat treatment process.The morphological structure,elemental composition,crystalline phases,and optical properties of the membrane were studied in detail by field‐emission scanning electron microscopy,transmission electron microscopy,X‐ray photoelectron spectroscopy,X‐ray diffraction,and ultraviolet‐visible spectroscopy.Compared with that of a pure Na2Ti6O13membrane,the Au‐Cu(I)@Na2Ti6O13membrane displayed much higher photocatalytic activity for the decomposition of acetaldehyde,a typical volatile organic compound,under visible light illumination.It was found that the photocatalytic activity of the Au‐Cu(I)@Na2Ti6O13membrane increased as the amount of Au was increased.The membrane loaded with2.85wt%Au showed the highest photocatalytic activity in the decomposition of acetaldehyde of the investigated materials.We found that in the photocatalyst membrane,Na2Ti6O13acted as a support material,Au displayed plasmonic absorption,and Cu(I)behaved as a co‐catalyst.The present membrane materials can avoid the self‐aggregation typically observed during the course of photocatalytic reactions.As a result,they can be easily separated,recycled,and reactivated after their practical application,making these functional materials attractive for use in air cleaning applications.
文摘The click reaction is one of the latest techniques for the functional analysis of bioactive compounds and the analysis makes novel concepts and strategies for medicinal chemistry. N-methylated glycine derivatives have inhibitory activity for the click reaction in direct Cu(I) system because of decrease of Cu(I) concentration. The Cu(I) concentration recovered effectively by sodium ascorbate. Quantitative determination of click reaction at various ligand concentrations revealed that the decrease in reaction yields was observed in a substrate concentration-dependent manner.
基金Supported by the Young Talent Program of Fujian Province (No. 2007F3117)Natural Science Foundation of Fujian Province (No. 2007J0001)
文摘An unusual 3D porous network assembled by tridentate ligand Tbmiz [1,3,5- tris（benzimidazol-1-ylmethyl）-2,4,6-trimethylbenzene] and Cu-I cluster was synthesized by means of hydrothermal process. It crystallizes in the trigonal system, space group P-3c1 with a = 14.2362（8）, b = 14.2362（8）, c = 36.4017（35）A, γ = 120.00°, V = 6389.1（8）, Dc = 1.976 g/cm^3, Z = 2, μ（MoKα） = 0.71073 and F（000） = 3692.0. Of the 40832 total reflections, 3948 were unique （Rint = 0.0366）. The final R = 0.0460 and wR = 0.1335 for 3948 observed reflections with I 〉 2σ（I）.
基金supported by the National Natural Science Foundation of China(21490571,21222402,21174120)the Key Project of the Ministry of Science and Technology of China(2013CB834702)+1 种基金the Research Grants Council of Hong Kong(604711,602212,604913)Anjun Qin and Benzhong Tang thank the support from Guangdong Innovative Research Team Program(201101C0105067115)
文摘An air-stable supported Cu(I) catalyst, Cu I@PS-Phen, was designed and synthesized. Cu I@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable polytriazoles with high molecular weights(Mw up to 30800), and low copper residue content(down to 190 ppm) in high yields(up to 94.2%) under mild reaction conditions without the exclusion of oxygen.
文摘In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(Ⅰ) coordination polymer [CuI(DBBD)_2]_n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P21, and a=0.881 30(19) nm, b=1.966 0(6) nm, c=1.478 1(4) nm, β=119.429(12)°, V=2.230 5(10) nm3, Dc=1.276 g·cm-3. The crystal 2 belongs to orthogonal system with space group Fmm2, and a=2.044 41(17) nm, b=1.543 06(13) nm, c=1.652 45(13) nm, V=5.212 9(7) nm3, Dc=1.669 g·cm-3, Z=8. CCDC: 292931, 1; 292934, 2.
