• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.612-616
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• 1996

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate (BDDT2-), has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and characterized. In order to investigate the detailed electronic structure of the metal complexes of the new ligand, BDDT2-, in terms of the oxidation state of the central metal ions, we have carried out molecular orbital (MO) calculations of Ni(BDDT)2-and Cu(BDDT)2- utilizing an Extended Huckel method. Cyclic voltammetry data for both complexes were obtained with a potentiostat. We have also compared these results to the previously synthesized Ni(PDDT)2-, Ni(DDDT)2-,Cu(PDDT)2-, and Cu(DDDT)2-.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2043-2048
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• 2014

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.301-304
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• 2012

• 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

• Bulletin of the Korean Chemical Society
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• v.11 no.2
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• pp.85-88
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• 1990

The electron paramagnetic resonance (EPR) spectrum of the copper (II) complex with the 2-methylamino-1-cyclo-pentene-1-dithiocarboxylate (acdc) anion, $Cu(N-CH_3acdc)_2$ has been studied in the diamagnetic host lattices afforded by the corresponding divalent nickel, zinc, cadmium and mercury complexes. EPR parameters of the complex support the exclusive use of sulfur atoms by the ligand in metal binding. A combination of host lattice structure and covalency effects can be account for the observed spin-Hamiltonian parameters.

• Economic and Environmental Geology
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• v.42 no.1
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• pp.1-8
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• 2009

The Haman mineralized area is located within the Cretaceous Gyeongsang Basin along the southeastern part of the Korean peninsula. Almost all occurrences in the Haman area are representative of copper-bearing polymetallic hydrothermal vein-type mineralization. Within the area are a number of fissure-filling hydrothermal veins which contain tourmaline, quartz and carbonates with Fe-oxide, base-metal sulfide and sulfosalt minerals. The Gunbuk, Jeilgunbuk and Haman mines are each located on such veins. The ore and gangue mineral paragenesis can be divided into three distinct stages: Stage I, tourmaline + quartz + Fe-Cu ore mineralization; Stage II, quartz + sulfides + sulfosalts + carbonates; Stage III, barren calcite. Equilibrium thermodynamic data combined with mineral paragenesis indicate that copper minerals precipitated mainly within a temperature range of $350^{\circ}C$ to $250^{\circ}C$. During early mineralization at $350^{\circ}C$, significant amounts of copper ($10^3$ to $10^2\;ppm$) could be dissolved in weakly acid NaCl solutions. For late mineralization at $250^{\circ}C$, about $10^0$ to $10^{-1}\;ppm$ copper could be dissolved. Equilibrium thermodynamic interpretation indicates that the copper in the Haman-Gunbuk systems could have been transported as a chloride complex and the copper precipitation occurred as a result of cooling accompanied by changes in the geochemical environments ($fs_2$, $fo_2$, pH, etc.) resulting in decrease of solubility of copper chloride complexes.

• Fibers and Polymers
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• v.7 no.1
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• pp.30-35
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• 2006

The influences of a series of new azo direct dyes including copper-complexes based on benzidine congeners, 2,2'-dimethyl-5,5'-dipropoxybenzidine and 5,5'-dipropoxybenzidine, were examined using microorganism, Daphnia magna. The purpose of the research described in this paper was to use bioassays with daphnids to determine the aquatic toxicity of new azo dyes in which copper was incorporated. The results clearly show that copper has negative effects to aquatic ecosystem as expected. The study also suggested that the assay with Daphnia magna was an excellent method to evaluate the influences of dyes to the aquatic environment.

• Journal of the Korean institute of surface engineering
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• v.25 no.4
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• pp.173-180
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• 1992

The effects of the stabilizing additives such as NaCN, 2-MBT and Thiourea on bath decom-position, plating rate and surface morphology have been studied. Bath stability was increased in the order of an additive-free bath, and NaCN-, 2-MBT-, and Thiourea-stabilized baths. The sta-bilizing effects may be attributed to the stability of Cu(II) -complexes. The plating rate is the re-verse order of the bath stability. Accelerative effect of 2-MBT in proper quantity(0.3mg/$\ell$) may be explained by visualizing it absorbed through benzene ring or sulfur atom on portions of the sub-strates. The strong bond of the complexing part of the molecule to nearby chelated copper ions would tend to accelerate plating by making it easier for the Cu2+ -ligand bond to be broken. Sur-face morphologies of copper deposits depend on the bath additives. Electroless copper deposits from the 2-MBT stabilized baths are finer than the deposits from the NaCN- and Thiourea- stabi-lized baths due to the strong adsorption on the substrates.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.331-334
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• 1996

New copper(Ⅱ) complex of the pentaaza non-macrocyclic ligand 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl)-1,3-diazacyclohexane (2) and a dinuclear copper(Ⅱ) compex of the bis(macrocyclic) ligand 3, in which two 1,5,8,10,12,15-hexaazabicyclo[11.3.11.5]heptadecane subunits are linked together by an ethylene chain through the uncoordinated nitrogen (N10) atoms, have been prepared selectively by the reaction of the metal ion, 1,4,8-triazaoctane, ethylenediamine, and formaldehyde. The dinuclear complex [Cu2(3)]4+ has been also prepared by the reaction of [Cu(2)]2+ with ethylenediamine and formaldehyde. The reaction products largely depend on the molar ratio of the reactants employed. The mononuclear complex or each macrocyclic subunit of the dinuclear complex contains one 1,3-diazacyclohexane ring and has a square-planar geometry with a 5-6-5 or 5-6-5-6 chelate ring sequence. In acidic solution, the copper(Ⅱ) complex of 2 dissociates more slowly than those of other related non-cyclic polyamines.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2565-2570
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• 2011

The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{10}$) containing a N-$CH_2$-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo-[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{11}$). The mono-N-functionalized macrocyclic complexes $[ML^2]^{2+}$ (M = Ni(II) or Cu(II); $L^2$ = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^{7.12}$]docosane) can be prepared by the reaction of $L^{11}$ with nickel(II) or copper(II) ion in acetonitrile. The N-$CH_2CN$ group attached to $[ML^2]^{2+}$ readily reacts with water or methanol to yield the corresponding complexes of $HL^3$ bearing one N-$CH_2CONH_2$ pendant arm or $L^4$ bearing one $N-CH_2C(=NH)OCH_3$ group. The $N-CH_2CONH_2$ or $N-CH_2C(=NH)OCH_3$ group of each complex is coordinated to the central metal ion. Both $[NiL^4(H_2O)]^{2+}$ and $[CuL^4]^{2+}$ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield $[Ni(HL^3)(H_2O)]^{2+}$ or $[Cu(HL^3)]^{2+}$ in basic aqueous solutions. In contrast to $[Cu(HL^3)]^{2+}$, $[Ni(HL^3) (H_2O)]^{2+}$ is readily deprotonated to form $[NiL^3 (H_2O)]^+$ ($L^3$ = a deprotonated form of $HL^3$) in basic aqueous solutions.