• Journal of the Korean Chemical Society
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• v.18 no.1
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• pp.31-39
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• 1974

Solutions of $Mn^{++}, Co^{++} and Zn^{++}$ were mixed with various dibasic organic acids in the presence of cation exchange resin at room temperature. The distribution ratios of the metal ions between resin and solution were measured, using radioactive metal ions as tracer. From the observed variation of the distribution ratios with acid anion concentrations, it was concluded that $Mn^{++}, Co^{++}$ and $Zn^{++}$ formed one-to-one complexes with succinate, malonate, o-phthalate and tartrate ions in aqueous, 20 % ethanol-water and 20 % acetone-water solutions. The results of the present investigation indicated that the relative stabilities of the complexes increased in the order: $Mn^{++} < Co^{++} < Zn^{++} complexes, Succinate < malonate < o-phthalate < tartrate complexes, Aqueous < mixed solvent systems.$

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1036-1042
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• 1998

The preconcentration and determination of trace elements in water samples were studied by a solvent sublation utilizing dithizonate complexation. After metal dithizonates were formed, trace amounts of cadmium, cobalt, copper and lead were floated and extracted into small volume of a water-immiscible organic solvent on the surface of sample solution and determined in the solvent directly by GF-AAS. Several experimental conditions as formation condition of metal-dithizonate complexes, pH of solution, amount of dithizone, stirring time, the type and amount of surfactants, N2 bubbling rate and so on were optimized for the complete formation and effective flotation of the complexes. And also four kinds of light solvents were compared each other to extract the floated complexes, effectively. After the pH was adjusted to 4.0 with 5 M HNO3, 8.0 mL of 0.05% acetone solution of dithizone was added to 1.00 L water sample. The dithizonate complexes were flotated and extracted into the upper methyl isobutylketone (MIBK) layer by the addition of 2.0 mL 0.2% ethanolic sodium lauryl sulfate solution and with the aid of small nitrogen gas bubbles. And this solvent sublation method was applied to the analysis of real water samples and good results of more than 85% recoveries were obtained in spiked samples.

• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.302-308
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• 1994

Homogeneous catalytic oxidation of hydrazobenzene was investigated by employing pentadentate Schiff base complexes such as [Co(II)(Sal-DPT)(H$_2$O)] and [Co(II)(Sal-DET)(H$_2$O)] in oxygen-saturated methanol solvent. The oxidation product of hydrazobenzene(H$_2$AB) was trans-azobenzene(trans-AB). The rate constants of oxidation reaction measured by UV-visible spectrophotometry were observed as $6.06{\times}10^{-3}sec^{-1}$ for [Co(II)(Sal-DPT)(H$_2$O)] and $2.50{\times}10^{-3}sec^{-1}$ for [Co(II)(Sal-DET)(H$_2$O)]. The mechanism of oxidation reaction for H$_2$AB by homogeneous activated catalysts has been proposed as following. H$_2$AB + Co(II)(L)(H$_2$O) + O$_2$ $\rightleftharpoons^K_{MeOH}Co(III)(L)O_2{\cdot}H_2AB + H_2O\longrightarrow^{k}Co(II)(L) + trans-AB + H_2O_2$ (L: Sal-DPT and Sal-DET)

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.84-89
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• 1986

A newflexible $N_2O_2$-type tetradentate ligand. Ethylenediamine-N,N'-di-${\alpha}$-isobutyric acid(eddib), has been synthesized, and dichloro cobalt(III) complex of eddib has been prepared via the air-oxidation technique. Only S-cis isomer has been yielded during the preparation of complex. Ring strain and steric hinderance are cited as the cause for the preference for the S-cis geometric configuration. On series of cobalt(III) complexes of eddib, $[Co(eddib)L]^{n+}$ $(L = Cl{\cdot}(H_2O),\;CO_3^{2-},\;(H_2O)_2)$have been prepared in situ. In their electronic absorption spectra, the absorption maxima and their intensities of the above series of complexes are on the ordinary line of the spectrochemical and hyperchromic series. Elemental analysis, IR, NMR and electronic absorption spectra have been used to characterize the complex and geometries of the complex.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.367-375
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• 2016

A novel strategy for the synthesis of $CoSb_2$ nanoparticles is demonstrated via preparation of novel organometallic complexes. Hydrated cobalt oleate (CoOl) and non-hydrated antimony oleate (SbOl) complexes are synthesized as precursors. The $CoSb_2$ nanoparticles are prepared by hot injection, which involves thermolysis of CoOl and SbOl in a non-coordinating solvent at $320^{\circ}C$. The coordination modes and distinct thermal behaviors of the intermediate non-hydrated SbOl complexes are comparatively investigated by thermo-analytical techniques. When the reaction temperature is increased, the particle size is found to increase linearly. The crystallinity of the $CoSb_2$ nanoparticles prepared at $250^{\circ}C$ is amorphous phase without any peaks. $CoSb_2$ structural peaks start to appear at $300^{\circ}C$ and dominant peaks with high crystallinity are synthesized at $320^{\circ}C$. The potential chemical structures of non-hydrated SbOl and their reaction mechanisms by thermolysis are elucidated. The elemental composition and crystallographic structure of $CoSb_2$ nanoparticles suggest a bimodal interaction of the organic shell and the nanoparticle surface, with a chemical absorbed inner layer and physically absorbed outer layer of carboxylic acid.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2544-2548
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• 2011

Two pyridinecarboxamide cobalt dicyanide building blocks and Mn(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three trinuclear cyanide-bridged $Co^{III}-Mn^{II}$ complexes: $\{[Mn(MeOH)_4][Co(bpb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (1), $\{[Mn(MeOH)_4][Co(bpmb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (2) and $\{[Mn(DMF)_2(en)_2][Co(bpb)(CN)_2]_2\}{\cdot}2DMF{\cdot}H_2O$ (3) ($bpb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, en = ethylenediamine). Single crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. For complex 3, it was further linked into one-dimensional structure by ethylenediamine acting as bridges. Investigation of the magnetic properties of complex 3 reveals weak antiferromagnetic coupling between the neighboring Mn(II) centers through the bridging ethylenediamine molecule. A best-fit to the magnetic susceptibilities of complex 3 gave the magnetic coupling constant J = -0.073(2) $cm^{-1}$.

• Journal of the Korean Chemical Society
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• v.45 no.3
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• pp.213-218
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• 2001

The reaction of peroxo vanadium(V) complexes, $VO(O_2)_2(pic)^{2-}$, $VO(O_2)(nta)^{2-}$, and $VO(O_2)(dipic)^-$ with thiolato-cobalt(III), $(en)_2Co(SCH_2CH_2NH_2)^{2+}$ resulted in an oxygen-atom transfer in aqueous solutions. Rate constants ($M^{-1}S^{-1}$) for these reactions were (35$\pm$1), $(4.8{\pm}0.4){\times}10^{-2}$ , and $(8.6{\pm}0.5){\times}10^{-4}$, respectively. The coordinate peroxide was activated in the oxygen-atom-transfer reaction of $VO(O_2)_2(pic)^{2-}$, but it is not the case for VO(O$_2$) $(nta)^{2-}$ and VO(O$_2$) $(dipic)^-$. In this paper, we proposed that the direct attack of an electrophilic peroxide to a nucleophilic substrate occurs in the oxygen-atom transfer pathway of peroxo vanadium(V) complexes.

• Journal of the Korean Chemical Society
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• v.58 no.3
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• pp.258-266
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• 2014

Single crystals of cobalt(II) and nickel(II) complexes of 4-nitrobenzoic acid have been successfully grown by gel diffusion technique. The grown crystals were characterized by elemental analysis, FT-IR and UV-Visible spectroscopy. The structure of the grown crystals was elucidated using single crystal X-ray diffraction studies. The title compounds $[Co(Pnba)_2(H_2O)_4]{\cdot}2H_2O$ 1 and $[Ni(Pnba)_2(H_2O)_4]{\cdot}2H_2O$ 2 where PnbaH=4-nitrobenzoic acid, crystallize in centrosymmetric triclinic space group P-1. Magnetic susceptibility measurements reveal that the compounds are paramagnetic in nature. The mechanical strength of the grown crystals was determined by Vicker's microhardness studies. The ligand (4-nitrobenzoic acid) and the complexes have been screened for their biological activity against various bacteria and fungi. The activity data show that the biological activity of the complexes is higher than that of the ligand.

• Bulletin of the Korean Chemical Society
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• v.20 no.6
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• pp.648-652
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• 1999

Studies have been carried out on the unusual molecular nonrigidity of CoⅢ(PymS)3 and Cp* RhⅢ(PymS)2(PymS:2-mercaptopyrimidine). The crystal structure of CoⅢ(PymS)3 approximates to an octahedral mer isomer with 4-membered N-Schelating fashion. For Cp*RhⅢ(PymS)2, one PymS ligand bonds to the rhodium ion in an S-monodentate mode (Rh-S(2) = 2.366(1)Å) while the other ligand chelates to the metal ion in an N,S-bidentae mode (Rh-S(1)=2.414(1);Rh-N(1)=2.103(3)Å). Even though the conformations and configurations of both complexes are still retained in solution, an unusual nonrigidity for the protons of the PymS region is obsered in the solution. The broad proton signals of CoⅢ(PymS)3 exhibit a temperature-dependence in the range of -40∼40℃ with a free energy of activation ΔG=64.49kJ/mol(40℃). For Cp*RhⅢ(PymS)₂,such a fluxionality has been markedly observed in solution. This fluxional behavior can be explained in terms of "ligand tautomerism" in metal complexes containing potential tautomeric forms.

• Analytical Science and Technology
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• v.12 no.6
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• pp.498-503
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• 1999

Co(II), Ni(II), and Cu(II) complexes with tetradentate schiff base-$NOTDH_2$, were synthesized. The structures of these complexes were characterized by elemental analysis, IR, UV-visible, NMR spectra, and thermogravimetric analysis. The mole ratio of schiff base($NOTDH_2$) to the metal(II) at complexes was found to be 1:1. Cu(II) complexes were four-coordinated configuration, while Co(II) and Ni(II) complexes were hexacoordinated configuration containing two water molecules and all complexes were non-ionic compounds.