Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'...Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.展开更多
Ferrate（VI） was employed for the oxidation of cyanide （CN） and simultaneous removal of copper or nickel in the mixed/complexed systems of CN-Cu, CN-Ni, or CN-Cu-Ni. The degradation of CN （1.00 mmol/L） and remova...Ferrate（VI） was employed for the oxidation of cyanide （CN） and simultaneous removal of copper or nickel in the mixed/complexed systems of CN-Cu, CN-Ni, or CN-Cu-Ni. The degradation of CN （1.00 mmol/L） and removal of Cu （0.095 mmol/L） were investigated as a function of Fe（Ⅵ） doses from 0.3-2.00 mmol/L at pH 10.0. It was found that Fe（Ⅵ） could readily oxidize CN and the reduction of Fe（Ⅵ） into Fe（Ⅲ） might serve efficiently for the removal of free copper ions. The increase in Fe（Ⅵ） dose apparently favoured the CN oxidation as well as Cu removal. Moreover, the pH dependence study （pH 10.0-13.0） revealed that the oxidation of CN was almost unaffected in the studied pH range （10.0-13.0）, however, the maximum removal efficiency of Cu was obtained at pH 13.0. Similarly, treatment was carded out for CN-Ni system having the initial Ni concentration of 0.170 mmol/L and CN concentration of 1.00 mmol with Fe（Ⅵ） dose 2.00 mmol at various pH values （10.0-12.0）. Results showed a partial oxidation of CN and partial removal of Ni. It can be observed that Fe（Ⅵ） can partially degrade the CN-Ni complex in this pH range. Further, Fe（Ⅵ） was applied for the treatment of simulated industrial waste/effluent waters treatment containing CN, Cu, and Ni.展开更多
Metal complex, bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthrline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarrbo dithioate)copper(I)], was synthesized from the reaction of Schiff base, (2,2’)-dimethyl 2,2’-(1,1...Metal complex, bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthrline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarrbo dithioate)copper(I)], was synthesized from the reaction of Schiff base, (2,2’)-dimethyl 2,2’-(1,10-phenanthroline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarbo dithioate) and CuCl2 at reflux condition in methanol. The copper centers of the complex appear to be reduced. This probably was facilitated by in situ oxidative formation of disulfide bond at the uncomplexed ligand moieties. Single crystal X-ray diffraction analysis reveals the distorted tetrahedral geometry around the copper centers. This compound crystallizes in the triclinic space group, P-1 with crystallographic parameters: a = 10.006(3) ?, b = 13.272(3) ?, c = 22.123(6) ?, α = 85.656(6)°, β = 81.656(6)°, γ = 73.097(5)°, μ = 1.223 mm-1 , V = 2779.5(13) ?3, Z = 2, Dc = 1.437 Mg/m3, T = 293 (2) K.展开更多
The chelate complex of Cu2＋ with 2-hydroxy-（4-methylthio）butanoate（MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA） is an e...The chelate complex of Cu2＋ with 2-hydroxy-（4-methylthio）butanoate（MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA） is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure（C10H18Cu O6S2, 1, monoclinic, space group P21/c, Z = 2, a = 16.158（4）, b = 4.9733（12）, c = 9.159（2） ？, β = 104.786（4）°） exhibits that two MHA-H ligands coordinate with a CuII ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.展开更多
Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIT-4PyPh)}<sub>2</sub>(<strong>1</strong>) and [Cu(hfac)<sub>2</sub>][(NIT-3...Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIT-4PyPh)}<sub>2</sub>(<strong>1</strong>) and [Cu(hfac)<sub>2</sub>][(NIT-3PyPh)<sub>2</sub>](<strong>2</strong>)(NIT-4PyPh=2-[4-(4-pyridinylmethoxy) phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,NIT-3PyPh=2-[4-(3-pyridinylmethoxy)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,hfac=hexafluoroacetylacetone), have been synthesized and characterized. The X-ray crystal structure analyses show that structures of the two complexes are different. Complex <strong>1</strong> crystallizes in cyclic metal-radical dimer consisting of four Cu(hfac)<sub>2</sub> and two NIT-4PyPh ligands;four Cu(II) atoms adopt two coordinated modes. In the ring, each Cu(II) ion is hexa-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) and one nitrogen atom of the pyridinyl group from two different radicals. Outside the ring, each Cu(II) is penta-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) from the radical ligand. Complex <strong>2</strong> crystallizes in discrete molecule, while the Cu(II) atom is hexa-coordinated by four oxygen atoms of two hfac molecules and two nitrogen atoms of the pyridinyl group from two radical ligands.展开更多
文摘Dibenzoyl peroxide undergoes oxidative addition on metallic copper powder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol and tetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1) and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methods and Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7), b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055 Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4), b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055, Rw=0.062.
基金supported by the grant of the Basic Research Program of the Korea Science & Engineering Foundation (No R01-2006-000-10284-0)
文摘Ferrate（VI） was employed for the oxidation of cyanide （CN） and simultaneous removal of copper or nickel in the mixed/complexed systems of CN-Cu, CN-Ni, or CN-Cu-Ni. The degradation of CN （1.00 mmol/L） and removal of Cu （0.095 mmol/L） were investigated as a function of Fe（Ⅵ） doses from 0.3-2.00 mmol/L at pH 10.0. It was found that Fe（Ⅵ） could readily oxidize CN and the reduction of Fe（Ⅵ） into Fe（Ⅲ） might serve efficiently for the removal of free copper ions. The increase in Fe（Ⅵ） dose apparently favoured the CN oxidation as well as Cu removal. Moreover, the pH dependence study （pH 10.0-13.0） revealed that the oxidation of CN was almost unaffected in the studied pH range （10.0-13.0）, however, the maximum removal efficiency of Cu was obtained at pH 13.0. Similarly, treatment was carded out for CN-Ni system having the initial Ni concentration of 0.170 mmol/L and CN concentration of 1.00 mmol with Fe（Ⅵ） dose 2.00 mmol at various pH values （10.0-12.0）. Results showed a partial oxidation of CN and partial removal of Ni. It can be observed that Fe（Ⅵ） can partially degrade the CN-Ni complex in this pH range. Further, Fe（Ⅵ） was applied for the treatment of simulated industrial waste/effluent waters treatment containing CN, Cu, and Ni.
文摘Metal complex, bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthrline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarrbo dithioate)copper(I)], was synthesized from the reaction of Schiff base, (2,2’)-dimethyl 2,2’-(1,10-phenanthroline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarbo dithioate) and CuCl2 at reflux condition in methanol. The copper centers of the complex appear to be reduced. This probably was facilitated by in situ oxidative formation of disulfide bond at the uncomplexed ligand moieties. Single crystal X-ray diffraction analysis reveals the distorted tetrahedral geometry around the copper centers. This compound crystallizes in the triclinic space group, P-1 with crystallographic parameters: a = 10.006(3) ?, b = 13.272(3) ?, c = 22.123(6) ?, α = 85.656(6)°, β = 81.656(6)°, γ = 73.097(5)°, μ = 1.223 mm-1 , V = 2779.5(13) ?3, Z = 2, Dc = 1.437 Mg/m3, T = 293 (2) K.
基金supported by the National Natural Science Foundation of China (No. 21301139,21373158,21103135,51304158)Scientific Research Program Funded by Shaanxi Provincial Education Department (No. 2013JK0651)+1 种基金the Scientific Research Cultivating Fund (No. 201221)the Doctoral Starting Fund (No. 2014QDJ004) from Xi'an University of Science and Technology
文摘The chelate complex of Cu2＋ with 2-hydroxy-（4-methylthio）butanoate（MHA-H, the anion derived from the so-called methionine hydroxy-analogue, largely used in animal nutrition as a source of methionine, MHA） is an efficient, bioavailable trace mineral additive for animal feeding. The structure of MHA-H copper chelate was investigated by single-crystal X-ray diffraction. The crystal structure（C10H18Cu O6S2, 1, monoclinic, space group P21/c, Z = 2, a = 16.158（4）, b = 4.9733（12）, c = 9.159（2） ？, β = 104.786（4）°） exhibits that two MHA-H ligands coordinate with a CuII ion to form a square-planar environment completed to an octahedron through interaction with carbonyl oxygens of neighboring molecules, which expand to constitute a two-dimensional sheet coordination network. And a separation between the hydrophilic and lipophilic moieties like micelles was found in the packing structure. X-ray powder diffraction and thermogravimetric analysis were used to study the phase purity of the bulk sample and thermostability of complex 1, respectively.
文摘Two new nitronyl nitroxide Cu(II) complexes {[Cu(hfac)<sub>2</sub>]<sub>2</sub>(NIT-4PyPh)}<sub>2</sub>(<strong>1</strong>) and [Cu(hfac)<sub>2</sub>][(NIT-3PyPh)<sub>2</sub>](<strong>2</strong>)(NIT-4PyPh=2-[4-(4-pyridinylmethoxy) phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,NIT-3PyPh=2-[4-(3-pyridinylmethoxy)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide,hfac=hexafluoroacetylacetone), have been synthesized and characterized. The X-ray crystal structure analyses show that structures of the two complexes are different. Complex <strong>1</strong> crystallizes in cyclic metal-radical dimer consisting of four Cu(hfac)<sub>2</sub> and two NIT-4PyPh ligands;four Cu(II) atoms adopt two coordinated modes. In the ring, each Cu(II) ion is hexa-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) and one nitrogen atom of the pyridinyl group from two different radicals. Outside the ring, each Cu(II) is penta-coordinated by four oxygen atoms of two hfac ligands and one oxygen atom (ONCNO) from the radical ligand. Complex <strong>2</strong> crystallizes in discrete molecule, while the Cu(II) atom is hexa-coordinated by four oxygen atoms of two hfac molecules and two nitrogen atoms of the pyridinyl group from two radical ligands.
