The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentrati...The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.展开更多
The solvent extraction of copper from simulated ammoniacal spent etchant with 1-（4＇-dodecyl）-phenyl-3-tertiary butyl-1,3-octadione（HR） was studied,and a model of extraction isotherm was proposed and verified with...The solvent extraction of copper from simulated ammoniacal spent etchant with 1-（4＇-dodecyl）-phenyl-3-tertiary butyl-1,3-octadione（HR） was studied,and a model of extraction isotherm was proposed and verified with equilibrium extraction constant.The influence of equilibration time,extractant concentration and phase ratio on the extraction of copper was studied at（298±0.5） K.For the spent etching solutions containing 112.98 g/L Cu,6 mol/L NH3 and 1 mol/L NH4＋,the optimal solvent extraction condition of copper was obtained in one-stage solvent extraction at phase ratio of 5：4 with 40% HR in sulphonated kerosene for 5 min.The copper concentration in the raffinate decreased to 63.24 g/L and raffinate can be favorably recycled to the etching solution.The stripping studies were carried out with the simulated copper spent electrolyte containing 30 g/L Cu and 180 g/L H2SO4.The stripping ratio is 98.27% from the loaded organic phase after one-stage stripping at phase ratio of 1：2 at（298±0.5） K.展开更多
The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations....The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.展开更多
α-diketones and β-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield a-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al syst...α-diketones and β-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield a-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al system. The possible mechanisms are also discussed.展开更多
The reaction of anhydrous YbCl3 with lithium b-diketiminate, LLi (L = N,N- diphenyl-2,4-pentanediimine anion), in 1:1 molar ratio in THF gave rise to the title complex LYbCl2(THF)2 1 which has been characterized by si...The reaction of anhydrous YbCl3 with lithium b-diketiminate, LLi (L = N,N- diphenyl-2,4-pentanediimine anion), in 1:1 molar ratio in THF gave rise to the title complex LYbCl2(THF)2 1 which has been characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pna21(#33) with a = 19.657(8), b = 9.581(4), c = 14.107(6) ? V = 2656.8(18) 3, Z = 4, C25H33N2O2Cl2Yb, Mr = 637.49, Dc = 1.594 g/cm3, F(000) = 1268.00 and m(MoKa) = 3.744mm-1. The final R and wR are 0.031 and 0.073 for 2596 observed reflections with I > 2s(I), respectively. The X-ray crystal structure analysis revealed that the center ytterbium(III) is bonded to two chloride anions, two oxygen atoms from two tetrahydrofuran molecules and one chelate ligand b-diketiminate to form a six-coordinate distorted octahedral geometry.展开更多
Poly（ethylene glycol）-modified 13-diketone macroligand is developed to sensitize europium（III） ions in water. High lumines cence intensity characteristic of Eu3 was achieved due to spontaneous formation of micelle...Poly（ethylene glycol）-modified 13-diketone macroligand is developed to sensitize europium（III） ions in water. High lumines cence intensity characteristic of Eu3 was achieved due to spontaneous formation of micelle-like structure in which the hydro phobic core prevents luminescence-quenching by water molecules. The pH is found to induce a quantitative ratio change in two fluorescence bands from both ligand and Eu3.展开更多
The selectivities, including peri-, regio-, and diastereoselectivities, in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory （DFT） calcu...The selectivities, including peri-, regio-, and diastereoselectivities, in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory （DFT） calculation. The results indicate that vicinal diimines prefer stepwise [2＋2] cycloaddition rather than [2＋4] cycloaddition to generate cis-4-imino-β-lactams. The diimines attack the less sterically hindered exo-side of ketenes to generate zwitterionic intermediates, which directly undergo a conrota- tory ring closure to produce cis-4-imino-β-lactams whatever diimines with less or more bulky N-substituents. For unsymmetric vicinal ketoaldehyde-derived diimines, their ketimines attack the exo-side of ketenes and undergo a conrotatory ring closure to produce cis-4-aldimino-β-lactams due to less steric effect. The current theoretical studies provide very important information for in-depth understanding of the selective formation of mono-cis-β-lactams from vicinal diimines and ketenes.展开更多
基金Project (2007CB613601) supported by the National Basic Research Program of ChinaProject (CX2010B112) supported by Hunan Provincial Innovation Foundation for Postgraduate, China
文摘The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.
基金Project (2007CB613601) supported by the National Basic Research Program of China
文摘The solvent extraction of copper from simulated ammoniacal spent etchant with 1-（4＇-dodecyl）-phenyl-3-tertiary butyl-1,3-octadione（HR） was studied,and a model of extraction isotherm was proposed and verified with equilibrium extraction constant.The influence of equilibration time,extractant concentration and phase ratio on the extraction of copper was studied at（298±0.5） K.For the spent etching solutions containing 112.98 g/L Cu,6 mol/L NH3 and 1 mol/L NH4＋,the optimal solvent extraction condition of copper was obtained in one-stage solvent extraction at phase ratio of 5：4 with 40% HR in sulphonated kerosene for 5 min.The copper concentration in the raffinate decreased to 63.24 g/L and raffinate can be favorably recycled to the etching solution.The stripping studies were carried out with the simulated copper spent electrolyte containing 30 g/L Cu and 180 g/L H2SO4.The stripping ratio is 98.27% from the loaded organic phase after one-stage stripping at phase ratio of 1：2 at（298±0.5） K.
基金Supported by the National Natural Science Foundation of China （20776066, 20476044） and the Specialized Research Fund for the Doctoral Program of Higher Education of China （20060291002）.
文摘The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.
基金Project (No. 20072033) supported by the National Natural Science Foundation of China and the Specialized Research Fund for the Doctoral Program of Higher Education Ministry, China
文摘α-diketones and β-diketones react with Grignard reagents in the presence of a catalytic amount of Cp2TiCl2 to yield a-ketols and corresponding ketones respectively. Sulfoxides can be deoxygenated by Cp2TiCl2/Al system. The possible mechanisms are also discussed.
基金Supported by the National Natural Science Foundation of China (20072027) Department of Education of Jiangsu province and the Key Laboratory of Organic Synthesis of Jiangsu province
文摘The reaction of anhydrous YbCl3 with lithium b-diketiminate, LLi (L = N,N- diphenyl-2,4-pentanediimine anion), in 1:1 molar ratio in THF gave rise to the title complex LYbCl2(THF)2 1 which has been characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pna21(#33) with a = 19.657(8), b = 9.581(4), c = 14.107(6) ? V = 2656.8(18) 3, Z = 4, C25H33N2O2Cl2Yb, Mr = 637.49, Dc = 1.594 g/cm3, F(000) = 1268.00 and m(MoKa) = 3.744mm-1. The final R and wR are 0.031 and 0.073 for 2596 observed reflections with I > 2s(I), respectively. The X-ray crystal structure analysis revealed that the center ytterbium(III) is bonded to two chloride anions, two oxygen atoms from two tetrahydrofuran molecules and one chelate ligand b-diketiminate to form a six-coordinate distorted octahedral geometry.
基金supported by the National Natural Science Foundation of China (21222405)the Research Fund for the Doctoral Program from Ministry of Education (WJ2060200012)the Science and Technology Development Center
文摘Poly（ethylene glycol）-modified 13-diketone macroligand is developed to sensitize europium（III） ions in water. High lumines cence intensity characteristic of Eu3 was achieved due to spontaneous formation of micelle-like structure in which the hydro phobic core prevents luminescence-quenching by water molecules. The pH is found to induce a quantitative ratio change in two fluorescence bands from both ligand and Eu3.
文摘The selectivities, including peri-, regio-, and diastereoselectivities, in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory （DFT） calculation. The results indicate that vicinal diimines prefer stepwise [2＋2] cycloaddition rather than [2＋4] cycloaddition to generate cis-4-imino-β-lactams. The diimines attack the less sterically hindered exo-side of ketenes to generate zwitterionic intermediates, which directly undergo a conrota- tory ring closure to produce cis-4-imino-β-lactams whatever diimines with less or more bulky N-substituents. For unsymmetric vicinal ketoaldehyde-derived diimines, their ketimines attack the exo-side of ketenes and undergo a conrotatory ring closure to produce cis-4-aldimino-β-lactams due to less steric effect. The current theoretical studies provide very important information for in-depth understanding of the selective formation of mono-cis-β-lactams from vicinal diimines and ketenes.
