• Title/Summary/Keyword: Cobalt Complexes

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Adsorption characteristic of uranium(VI) on OenNtn synthetic resin with styrene (Styrene을 이용한 OenNtn수지의 합성과우라늄(VI) 이온 흡착 특성)

  • Kim, Joon-Tae
    • Journal of environmental and Sanitary engineering
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    • v.23 no.2
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    • pp.47-53
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    • 2008
  • The ion exchange resins have been synthesized from chloromethyl styrene (dangerous matter) 1, 4-divinylbenzene(DVB) with 1%, 5%, and 15%-crosslinked and macrocyclic ligand of cryptand type by copolymerization method and the adsorption of uranium(VI), cobalt(II) and europium(III) ions have been investigated in various experimental conditions. The correlation between the adsorption characteristics of rare earths and transition metal on the resins and stability constants of complexes with macrocyclic ligand have been examined. The uranium ion was not adsorbed on the resins below pH 2.0, but the power of adsorption of uranium ion increased rapidly above pH 3.0. The adsorption power was in the order of 1%, 5% and 15%-crosslinked resin, but adsorptive characteristics of resins decreased in proportion to the order of dielectric constants of solvents.

Molecular Switching Coordination Polymers. 4.4'-Chalcogenobispyridine Bridged Cobalt Benzoquinone Complexes

  • 조두환;정종화;여환진;손윤수;정옥상
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.504-507
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    • 1995
  • The reaction of Co2(CO)8 with 3,6-di-tert-butyl-1,2-benzoquinone in the presence of the respective 4,4'-chalcogenobispyridine results in the coordination polymers of [CoⅢ(4,4'-X(Py)2)(DBSQ)(DBCat)]n (X=S, Se, Te; Py=pyridine; DBSQ=3,6-di-tert-butylsemiquinone; DBCat=3,6-di-tert-butylcatechol). The title compounds undergo an intramolecular Cat → Co electron transfer, and thus change toward the [CoⅡ(4,4'-X(Py)2)(DBSQ)2]n at elevated temperature. The temperature-switching properties of the compounds directly depend upon the electronegativity of the chalcogen atom of the 4,4'-chalcogenobispyridine coligands. The spectroscopic data disclose that the properties of [CoⅢ(4,4'-S(Py)2)(DBSQ)(DBCat)]n and [CoⅢ(4,4'-Se(Py)2)(DBSQ)(DBCat)]n are similar each other in contrast to those of [CoⅢ(4,4'-Te(Py)2)(DBSQ)(DBCat)]n.

Bistability of $Co^{III}$(N-N)(3,6-DBSQ)(3,6-DBCat):Subtle Diimine Ligand Effect (N-N=4,7-Dimethyl-1,10-phenanthroline, 5-Chloro-1,10-phenanthroline;DBSQ=Di-tert-butylsemiquinonato;DBCat=Di-tert-butylcatecholato)

  • Ok-Sang Jung;Young-A Lee;Younkyoo Kim;Youn Soo Sohn
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.641-643
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    • 1994
  • Studies of Co(N-N)(3,6-DBSQ)(3,6-DBCat)(N-N=4,7-dimethyl-1 ,10-phenanthroline, 5-chloro-1,10-phenanthroline; DBSQ=di-tert-butylsemiquinonato; DBCat=di-tert-butylcatecholato) have been carried out on the bistability by intramolecular cobalt-quinone electron transfer in solid state. The title complexes dominantly exist as $Co^{III}$(N-N)(3,6-DBSQ)(3,6-DBCat) at room temperature and display a significant bistability on temperature variation. Subtle change in optical spectra and magnetic properties is observed when diimine ligands are changed.

Redox Chemistry and Valence Tautomerism of Cobalt-Quinone Complexes in Nonaqueous Solvents

  • 전승원;이현;이효경;최용국;정옥상
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.212-217
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    • 1998
  • The electrochemistry and valence tautomerism of CoⅢ(N-N)(SQ)(Cat), [N-N=N,N,N',N'-tetramethylethylenediamine (TMEDA); SQ=3,5- or 3,6-di-tert-butyl-semiquinone, Cat=3,5- or 3,6-di-tert-butyl-catechol], have been investigated by spectroscopic, electrochemical, spectroelectrochemical methods in nonaqueous solvents under anaerobic condition. The transition temperature between tautomers is dependent upon the donation effect of substituted quinone ligand and solvent. It increases with the increase of donation effect of solvent and quinone ligand. CoⅢ(TMEDA)(SQ)(Cat) is reduced to [CoⅡ(TMEDA)(SQ)(Cat)]-, and then reduces to [CoⅡ(TMEDA)(Cat)2]2-. CoⅢ(TMEDA)(SQ)(Cat) is oxidized to [CoⅢ(TMEDA)(SQ)2]+, but the stability of the oxidized form in DMF is dependent upon the solution temperature. With the increase of solution temperatrue the oxidized form may be converted to [CoⅡ(TMEDA)(SQ)(BQ)]+ by intramolecular electron transfer from SQ ligand to CoⅢ.

Dependence of Electronic Spectra on the Degree of Conjugation in Organocobalt(Ⅲ) Complexes (공액도에 따른 유기코발트 착화합물의 전자스펙트럼에 관한 연구)

  • Hye Kyung Seo;Chan Ah Bong;Young Ae Hwang Park
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.1047-1052
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    • 1993
  • The electronic spectra of enzyme-model organocobalt(Ⅲ) complexes containing completely or partially conjugated macrocyclic ligands were measured in various solvents to investigate the solvent effect on the charge transfer band for the axial cobalt-carbon bond by the extent of conjugation in the equatorial macrocyclic ring; completely conjugated, $CH_3CoL,\;C_6H_5CoL,\;CNCoL,\;CH_3CoL',\;CNCoL'$, partially conjugated $CH_3(py)Co(DH)_2, CH_3CoL"$, unconjugated dienes, $[CH_3Co(1,4-CT)](ClO_4)_2$, and open ring, $CH_3Co(salen)$. The position of the charge transfer band which corresponds to the cobalt-carbon bond was shifted to a shorter wavelength as the polarity of solvent increased and the transition energy $(E_T)$ had a linear relationship with solvent polarity parameter, Z-value, only in the case of completely conjugated system. However, the linear correlation between $E_T$and Z was not observed for partially conjugated and open ring systems.

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Effect of Metal Complexes as a Catalyst on Curing Behavior and Mechanical Properties of Silica Filled Epoxy-Anhydride Compounds (촉매로서 금속 착화합물이 실리카가 충전된 에폭시-산무수물 복합체의 경화 거동 및 물성에 미치는 영향)

  • Seo, Byeongho;Lee, Dong-Hoon;Lee, Noori;Do, Kiwon;Ma, Kyungnam;Kim, Wonho
    • Elastomers and Composites
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    • v.49 no.1
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    • pp.59-65
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    • 2014
  • In this study, in order to complete curing reaction of the molding compound comprising an epoxy/anhydride at $71^{\circ}C$ for 40 hours, metal coordination complexes such as cobalt (II) acetylacetonate, potassium acetylacetonate, iron (III) acetylacetonate and chromium (III) octoate as a catalyst were applied to the epoxy/anhydride compounds respectively. The weight ratio of an epoxy part/an anhydride part was adjusted to improve the mechanical properties of the molding compound. According to the experimental results, an epoxy/anhydride compound containing chromium (III) octoate showed a high conversion at $71^{\circ}C$ for 40 hours as well as a proper processability at room temperature among the several metal coordination complexes. For the mechanical properties of the cured epoxy/anhydride compound, the compounds containing weight ratio from 0.9/1 to 0.5/1 of the epoxy part/anhydride part with chromium (III) octoate showed the high flexural strength, and higher compressive strength was shown with increasing of the hardener part.

산소 첨가된 Cobalt(Ⅲ) 착물에 의한 2,6-di-tert-butylphenol의 산화반응

  • O, Jeong Geun;Im, Chae Pyeong;Choe, Yong Guk
    • Journal of the Korean Chemical Society
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    • v.46 no.3
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    • pp.219-224
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    • 2002
  • The oxidation reaction between 2,6-di-tert-butylphenol (DTBP) and oxygen adducted Co(III) complexes as a catalysis has been studied by UV-visible spectrophtometry. According to the results, main product is 2,6-di-tert-butylbenzoquinone(BQ) and the activity of the complexes is bigger in [Co(III)2(SMPD)2(Py)2]2O2 than in [Co(III)2(SPPD)2(Py)2]2O2. The rate constant is 4.55~2.12${\times}$10$-3}$s. It was found that the oxidation reaction is primary reac-tion or concentration of catalysis, O2 molecule and substance. The reasult is far from Arrhenius properties because acti-vationenergy is 10.38 kJ/mol.

Enantioselective Epoxide Synthesis on the Chiral Salen Catalyst having a Transitional Metal Salt (전이금속염 함유 키랄 살렌 촉매에 의한 광학선택적 에폭사이드의 합성)

  • Guo, Xiao-Feng;Kawthekar, Rahul B.;Kim, Geon-Joong
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.769-776
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    • 2008
  • The stereoselective synthesis of chiral terminal epoxide is of immense interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new chiral Co(salen) complexes bearing cobalt(II) chloride, iron(III) chloride and zinc(II) nitrate have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of terminal epoxides such as styrene oxide and phenylglycidylether by hydrolytic kinetic resolution technology and for the synthesis of glycidyl buthylate. The easily prepared complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ nucleophile, providing enantiomerically enriched terminal epoxides (>99% ee). The newly synthesized chiral salen showed remakablely enhanced reactivity with substantially low loadings. The system described in this work is very efficient for the sinthesis of chiral epoxide and 1,2-diol intermediates.

Iodine Sorption Complexes of Partially Cobalt(II) Exchanged Zeolite A. Two Crystal Structures of $Co_{3.5}Na_5Si_{12}Al_{12}O_{48}\cdot2.5I_2\;and\;Co_{3.5}Na_5Si_{12}Al_{12}O_{48}\cdot5.0I_2$

  • Kim, Yang;Lee, Suk-Hee;Seff, Karl
    • Bulletin of the Korean Chemical Society
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    • v.10 no.5
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    • pp.426-430
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    • 1989
  • Two crystal structures of iodine sorption complexes of dehydrated partially Co(Ⅱ )-exchanged zeolite A, $Co_{3.5}Na_5-A{\cdot}xI_2$, x = 2.5 and 5.0, have been determined by single crystal X-ray diffraction techniques. Both structures were solved and refined in cubic space group, Pm3m at $21(1)^{\circ}C$. The structures of $Co_{3.5}Na_5-A{\cdot}2.5I_2$(a = 12.173(1) ${\AA}$) and $Co_{3.5}Na_5-A{\cdot}5.0I_2$(a = 12.130(1) ${\AA}$) were refined to the final error indices, $R_1$ = 0.081 and $R_2$ = 0.077 with 261 reflections and $R_1$ = 0.103 and $R_2$ = 0.112 with 225 reflections, respectively, for which I>3${\sigma}$(I). In both structures, 3.5 $Co^{2+}$ ions and 4.5 $Na^+$ ions per unit cell lie at two crystallographically different 6-ring positions. 0.5 $Na^+$ ion lines in an 8-oxygen ring plane. Dehydrated $Co_{3.5}Na_5$-A sorbs 2.5 iodine molecules per unit cell at $70^{\circ}C$ (vapor pressure of $I_2$ is ca. 8.3 torr) within 30 minutes and 5 iodine molecules per unit cell at $80^{\circ}C$ (vapor pressure of $I_2$ is ca. 14.3 torr) within 24 hours. Each iodine molecule makes a close approach, along its axis to framework oxygen atom with I-I-O = $175^{\circ}$.

Studies on Amidoximated Acrylic Fiber(I) -Amidoximation and Adsorption Capacity to Transition Metals - (아크릴 섬유의 아미도옥심화에 관한 연구(I) -아미도옥심 반응과 천이금속의 흡착능-)

  • Chin, Young Gil;Kim, Kyu Beom
    • Textile Coloration and Finishing
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    • v.8 no.6
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    • pp.40-46
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    • 1996
  • In order to investigate a practical application of fibrous absorbents to transition metals such as copper, nickel, cobalt, chrome, and iron, amidoximated fiber as a particular class of solid chelate agents were prepared from acrylic fibers treatment with hydroxylamine. The adsorption mechanisms of metal ions onto amidoximated acrylic fibers and their complexes were studied. Amidoximation of acrylic fiber with hydroxylamine is found to be first-order reaction, followed by the disappearance of infrared adsorption peaks due to nitrile groups of acrylic fibers. The uptake of metal ions onto amidoximated acrylic fiber is increased with temperature raising and the adsorption is also depended on pH of the soiutions. About 70% of metal ions can be recovered from aqueous solutions of Ni(II), Co(II), Cr(III), and Fe(II) on the concentration below 5x 10$^$^{-4}$ in the range of pH 2.1~10.0. Transition metals are adsorbed to form complex with amidoxime group by the ligand sites such as C=N, NH, NO, NHOH.OH.

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