In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br...In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.展开更多
The interactions of the complexes of Cu(phen) 2+ 2 and Cu(bpy) 2+ 2 with DNA were investigated with electrochemistry and spectroelectrochemistry. Binding constants( K n + ) and the reaction model wer...The interactions of the complexes of Cu(phen) 2+ 2 and Cu(bpy) 2+ 2 with DNA were investigated with electrochemistry and spectroelectrochemistry. Binding constants( K n + ) and the reaction model were obtained from their electrochemical behavior and electrochemical data. The binding constants( K 2+ ) for Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were 8 51×10 3 L·mol -1 and 3 27×10 3 L·mol -1 , and K +s were 3 09×10 4 L·mol -1 and 5 66×10 3 L·mol -1 respectively. The spectroscopic characteristics of the complexes of Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were studied in detail. Some significant spectroelectrochemical data were obtained. The interaction of DNA with complexes was described.展开更多
A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and...A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 8.7110（9）, b = 14.7143（14）, c = 14.8507（15） A, β = 109.721（6）°, V = 1791.9（3） A3, Z = 4, Dc = 1.916 g/cm3, CI7H16CulN3S2, Mr = 516.89, λ（MoKa） = 0.71073A,μ = 3.178 mm^-1, F（000） = 1012, the final R = 0.0369 and wR = 0.0987. A total of 4082 unique reflections were collected, of which 2916 with I 〉 2σ（I） were observed. The Cu（Ⅱ） atom is five-coordinated in a distorted square-pyramidal geometry by one I atom in the apical position, two S atoms from a prdtc ligand and two N atoms from a phen ligand in the basal plane. There exist face-to-face aromatic π-π stacking interactions between adjacent phen ligands stabilizing the structure and making the complex assemble into a 1D structure along the a axis. It can be concluded that the difference of the dtc flexibility and reaction conditions result in the structural difference between complex 1 and CuI（dmdtc）（phen） （dmdtc = N, N-dimethyldithiocarbamate）.展开更多
[Zn（phen）3]·ZTO-6H2O（1） and [Cu（phen）3]·ZTO·6H2O（2） were synthesized by the reaction of ZnCNO3）2·6H2O/Cu（NO3）2·3H2O with 4,4-azo-1H-1,2,4-triazol-5-one（ZTO） and 1,10-phenanthrolin...[Zn（phen）3]·ZTO-6H2O（1） and [Cu（phen）3]·ZTO·6H2O（2） were synthesized by the reaction of ZnCNO3）2·6H2O/Cu（NO3）2·3H2O with 4,4-azo-1H-1,2,4-triazol-5-one（ZTO） and 1,10-phenanthroline（phen）. The two compounds were characterized by elemental analysis and IR spectrum analysis, respectively. Compound 1 was also characterized by single crystal X-ray diffraction analysis. For compound l, the coordination geometry around the Zn^2＋ is a distorted octahedron, with the bite angles of 76.7（3）°-77.6（4）° for all three phen ligands. Moreover, the thermal behaviors and thermal decomposition kinetics were studied and analyzed. Besides, thermal stability and safety parameters（TsADT, Tb） are 164.7 and 166.4℃ for compound 1, and 149.6 and 150.8℃ for compound 2, respectively.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
基金Supported by the National Natural Science Foundation of China(20936003,21276201)
文摘In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data.
文摘The interactions of the complexes of Cu(phen) 2+ 2 and Cu(bpy) 2+ 2 with DNA were investigated with electrochemistry and spectroelectrochemistry. Binding constants( K n + ) and the reaction model were obtained from their electrochemical behavior and electrochemical data. The binding constants( K 2+ ) for Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were 8 51×10 3 L·mol -1 and 3 27×10 3 L·mol -1 , and K +s were 3 09×10 4 L·mol -1 and 5 66×10 3 L·mol -1 respectively. The spectroscopic characteristics of the complexes of Cu(phen) 2+ 2 DNA and Cu(bpy) 2+ 2 DNA were studied in detail. Some significant spectroelectrochemical data were obtained. The interaction of DNA with complexes was described.
基金supported by the National Natural Science Foundation of China (Nos. 50572030 and 50372022)the Research Fund of Huaqiao University (No. 06BS216)the Young Talent Program of Fujian Province (No. 2007F3060)
文摘A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 8.7110（9）, b = 14.7143（14）, c = 14.8507（15） A, β = 109.721（6）°, V = 1791.9（3） A3, Z = 4, Dc = 1.916 g/cm3, CI7H16CulN3S2, Mr = 516.89, λ（MoKa） = 0.71073A,μ = 3.178 mm^-1, F（000） = 1012, the final R = 0.0369 and wR = 0.0987. A total of 4082 unique reflections were collected, of which 2916 with I 〉 2σ（I） were observed. The Cu（Ⅱ） atom is five-coordinated in a distorted square-pyramidal geometry by one I atom in the apical position, two S atoms from a prdtc ligand and two N atoms from a phen ligand in the basal plane. There exist face-to-face aromatic π-π stacking interactions between adjacent phen ligands stabilizing the structure and making the complex assemble into a 1D structure along the a axis. It can be concluded that the difference of the dtc flexibility and reaction conditions result in the structural difference between complex 1 and CuI（dmdtc）（phen） （dmdtc = N, N-dimethyldithiocarbamate）.
文摘[Zn（phen）3]·ZTO-6H2O（1） and [Cu（phen）3]·ZTO·6H2O（2） were synthesized by the reaction of ZnCNO3）2·6H2O/Cu（NO3）2·3H2O with 4,4-azo-1H-1,2,4-triazol-5-one（ZTO） and 1,10-phenanthroline（phen）. The two compounds were characterized by elemental analysis and IR spectrum analysis, respectively. Compound 1 was also characterized by single crystal X-ray diffraction analysis. For compound l, the coordination geometry around the Zn^2＋ is a distorted octahedron, with the bite angles of 76.7（3）°-77.6（4）° for all three phen ligands. Moreover, the thermal behaviors and thermal decomposition kinetics were studied and analyzed. Besides, thermal stability and safety parameters（TsADT, Tb） are 164.7 and 166.4℃ for compound 1, and 149.6 and 150.8℃ for compound 2, respectively.
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.
