• Korean Journal of Crystallography
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• v.17 no.2
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• pp.46-50
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• 2006

The dinuclear copper(II) complex {[Cu(pmea)Cl][Cu$(H_2O)_3]}Cl_2{\cdot} H_2O$ (1) (Hpmea=bis(2-pyridvlmethyl)amino-2-ethanoic acid) has been synthesized and characterized. It crystallizes in the monoclinic system $P2_1/c$, a=9.0008(6) ${\AA}$, b=28.0171(19) ${\AA}$, c=8.5590(6) ${\AA}$, $\beta$=104.2280(10)$^{\circ}$, V=2092.2(2) ${\AA}^3$, Z=4. Crystal structure of 1 reveals a syn-anti carboxylate-bridged dinuclear complex, in which the coordination environment around each copper atom exhibits a distorted square-pyramid and a distorted square plane, respectively.

• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.295-301
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• 1994

The Ru(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), and Pd(Ⅱ) complexes of N$_4$-polydentate ligands(meso-Me$_6$-[14]-ane, rac-Me$_6$-[14]-ane, and cyclam) have been prepared and their catalytic activity and selectivity in the oxidation of olefins in the presence of oxidant such as NaOCl, H$_2$O$_2$, t-BuOOH, and PhIO studied. The oxidations of cyclohexene, 1-hexene, cyclooctene, 1-octene, and styrene as substrates have been investigated gas chromatographically. The Ru(Ⅲ)-N$_4$ complexes showed high selectivity for epoxide in the catalyzed oxidation of olefins with NaOCl. The catalytic activities of Ru(Ⅲ)-N$_4$ complexes were discussed in terms of the flexibility of N$_4$-polydentate ligands, the Ru(Ⅲ)-Cl bond interaction and the steric effect of oxidants. The oxidation of 1-octene using PhIO as oxidant was carried out to verify. The Pd(Ⅱ) complex turned out to be more active catalyst than the Ni(Ⅱ) complexes.

• Journal of the Korean Chemical Society
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• v.35 no.5
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• pp.527-533
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• 1991

Template condensation reactions of formaldehyde with appropriate tetramines and diamines in the presence of N(II) or Cu(II) ion produce square planar complexes of hexaaza macrotricyclic and macrotetracyclic ligands $[M(L)]^{2+}$(M = Ni(II) or Cu(II); L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12,2,1,$1^{8,11}$]octadecane(C), 1,3,10,12,15,18-hexaazatetracyclo[16,2,1,$1^{12,15},0^{4,9}]$docosane(D) 4-methyl-1,3,6,8,12,15-hexaazatricyclo[13,3,1,$1^{8,12}$]eicosane(F), or 1,3,10,12,16,19-hexaazatetracyclo[l7,3,1,$1^{12,16},0^{4,9}]$tetracosane(G). These complexes contain two 1,3-diazacyclopentane or 1,3-diazacyclohexane rings in the six-membered chelate rings. The complexes of C and F contain one methyl group and those of D and G one cyclohexane ring in the five-membered chelate ring. Synthesis and characterization of the Ni(II) and Cu(II) complexes are presented. The effects of the ligand structure on the equilibrium $[Ni(L)]^{2+}2H_2O{\rightleftharpoons}[Ni(L)(H_2O)_2]^{2+}$ in aqueous solutions are described.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.405-409
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• 1991

The electrochemical behaviors of copper-1-(2-thiazolylazo)-2-naphthol [Cu(II)-TAN] complex in acetonitrile (AN) solution have been investigated by the use of polarography, controlled potential coulometry and UV-Vis spectroscopy. Cu(II)-TAN complex exhibit three reduction waves at -0.91 V, -1.34 V and -1.65 V vs. S.C.E. in acetonitrile solution containing 5.0 ${\times}\;10^{-3}$M tetraethylammonium perchlorate. Every reduction wave is diffusion controlled. The first reduction wave is considerably reversible and this process is attributed to the formation of anion radical. The second reduction process to the dianion is followed by a chemical reaction producing a complex of hydrazo complex. The third reduction process produce Cu(Hg) amalgam and amine compound.

• Journal of the Korean Chemical Society
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• v.42 no.1
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• pp.36-41
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• 1998

In this study, the extraction of Co(Ⅱ) and Cu(Ⅱ) into chloroform solution of dithizone, distribution ratios, extractabilities and extraction rate constants of the metal complexes were compared in each case with which thiocyanate ion was or not used as the auxiliary ligand. The use of the thiocyanate ion increased threefold the distribution ratio for Co(Ⅱ) complex in a basic solution and twofold for Cu(Ⅱ) complex in a wide pH range. And the extractability was also augmented from about 90 to 99 for Co(Ⅱ) and from 95 to 99 for Cu(Ⅱ) in a given period. The extraction rate constants were $k_1\;:\;1.2{\times}10^5$, $k_2\;:\;1.34{\times}10^{17}\; mol^{-1}dm^3s^{-1}$ in case of Co(Ⅱ) and$k_1\;:\;1.1{\times}10^8$, $k_2\;:\;2.83{\times}10^{10}\; mol^{-1}dm^3s^{-1}$ in case of Cu(Ⅱ) on the extraction of dithizonate complexes into chloroform solution.

• Analytical Science and Technology
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• v.8 no.3
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• pp.321-334
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• 1995

Basic studies for the effective extraction of ammonium pyrrolidine dithiocarbamate(APDC) complexes of Co(II), Ni(II) and Cu(II) into a solvent have been performed. The maximum distribution ratio was appeared (log D=1.3543) at pH 2.0 and the partition coefficient was 2.489 in the extraction of $4{\times}10^{-5}M$ APDC itself into chloroform. From the UV/visible spectra of metal-chelates in aqueous and organic solutions, the pH to form stable 1:2 metal-ligand complexes were Co(II):5.0, Ni(II):8.0 and Cu(II):8.0, respectively and only 1 minute was enough to be partitioned into the chloroform. Besides, the partition and extraction equilibria of the complexes were investigated by back-extracting $10.0{\mu}g/ml$ metal-chelates from the solvent into an aqueous solution beacuse of their slight solubilities in the aqueous solution. The distribution coefficients and extractabilities were as follows : at pH 6.5~8.5 of the aqueous solution, log D=2.834 : E(%)=99.9% for $Co(PDC)_2$, at pH 11, log D=5.699 E%=100 for $Ni( PDC)_2$, and at pH 6.0, log D=2.025 : E(%)=99.1% for $Cu(PDC)_2$. And the extraction and formation constants were log $K_{ex}=9.671$ : log ${\beta}_2=6.938$ for $Co(PDC)_2$, log $K_{ex}=9.646$ : log ${\beta}_2=7.071$ for $Ni( PDC)_2$, and log $K_{ex}=9.074$ : log ${\beta}_2=7.049$ for $Cu(PDC)_2$, respectively. From these results, an optimum extraction procedure can be constructed for the separative concentration of trace metallic ions, and the quantitative determination of them in advanced materials and environmental samples will be expected without any influence of sample matrixes.

• Journal of the Korean Chemical Society
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• v.47 no.2
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• pp.183-188
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• 2003

• Analytical Science and Technology
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• v.11 no.5
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• pp.341-346
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• 1998

2-Pyridinecarboxaldehyde thiocarbohydrazone(PyTC) have been reacted with $Cu^{2+}$ to form $[Cu(PyTC)H_2O)]SO_4$. This complex is soluble in water and polar organic solvents. The complex has been characterized by elemental analysis, conductivity, effective magnetic moment, and spectroscopic data. From the results the complex is square planar. The colorimetric determination of Cu(II) ion by using PyTC as a ligand was studied. The solution of copper(II) with PyTC was obeyed Beer's law in concentration up to $2.9{\times}10^{-4}M$ at pH 4.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.129-138
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• 1980

The formation constants of the mixed-ligand complexes in the Cd(II), Cu(II) and Pb(II)-Trien-OH system were studied by polarograph. The formation constant $(log{\beta}_{ij})$ was determined at $25^{\circ}C$ in the ionic strength of 0.1. It was also confirmed that the mixed ligand complexes in this system were formed above pH 10.2, 10.5 and 9.0 for Cu(II), Cd(II) and Pb(II) by the calculation of the distribution for complexes at the various pH. Masking of Cd(II) by conversion to anionic EDTA-complexes has been used to separate Cu(II) from Cd(II) through passage of a combined Trien-EDTA solution on an cationic resin column. The optimal condition for the separation of Cu(II) from Cd(II) is confirmed at the pH range above 9.0, not only by considering the theoretical equation of the conditional-exchange-constant of metal on the cation exchange resin,but also by calculating the distribution of the mixed ligand complexes in the resin at the various pH with computer. By analyzing the synthetic sample of Cu(II) and Cd(II) with a EDTA masking at pH 9.5, it is found that the results of the experiment are satisfied with the theoretical value.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.223-229
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• 1992

Mechanistic studies on the metal-exchange reactions of sparteine copper(II) dichloride [$SpCuCl_2$] with Hg(II) ion and Hg(0) metal have been carried out with the aid of Cyclic Voltammetry and UV-visible spectrophotometry. The metal exchange reaction of $SpCuCl_2$ with both Hg(II) ion and Hg(0) metal follows pseudo-first order kinetics. Rate constants and activation parameters of metal exchange reaction have been evaluated and reported. Experimental results indicate that the rate determining step for the exchange reaction is the cleavage of Cu(II)-N bond in the transient binuclear complex of Cu(II) and mercury(II) bound to sparteine ligand.