• Title/Summary/Keyword: Ligand Substitution

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Resin Synthesis of Adsorbent Uranium(VI) Ion using 1-Aza-18-Crown-6 (1-Aza-18-Crown-6를 이용한 우라늄(VI) 이온 흡착제 수지 합성)

  • Kim, Sun-Hwa;Kim, Hae-Jin
    • Journal of environmental and Sanitary engineering
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    • v.21 no.4 s.62
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    • pp.49-60
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    • 2006
  • The ion exchange resins have been synthesized from chlormethyl styrene - 1,4 - divinylbenzene(DVB) with 1%, 2%, 4% and 8%-crosslinking and 1-aza-18-crown-6 macrocyclic ligand by copolymerization method. Content of chlorine in styrene-DVB copolymer was decreased as crosslink increased and it is because as crosslink increased 1%, 2%, 4% and 8% DVB content increased and crosslink density increased and cavity was reduced. Functional group of resin almost disappeared as C-C1 peak around $700cm^{-1}$ was substituted with 1-aza-18-C-6 macrocyclic ligand and new peak of C-N around $1020cm^{-1}$ appeared, so it was confirmed that styrene-DVB copolymer and ligand were compounded. As crosslink increased in the analysis of element contents, it resulted in the reduction of nitrogen content and it is because as crosslink increased, it led to the reduction of chlorine content in the process of substitution reaction and it affected macrocyclic ligand substituted. Thermo analysis curve of functional synthetic resin decomposed three part of 1-aza-18-C-6, styrene, and DVB. Form of functional synthetic resin showed distortion of its particles as macrocyclic ligand was introduced to styrene-DVB copolymer and hydrogen of ligand caused substitution with chlorine element of styrene molecule.

Resin Synthesis of Adsorbent Metal Ions using 1-Aza-12-Crown-4 (1-Aza-12-Crown-4를 이용한 금속 이온 흡착제 수지 합성)

  • Kim Joon-Tae;Roh Gi-Hwan
    • Journal of environmental and Sanitary engineering
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    • v.19 no.3 s.53
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    • pp.52-57
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    • 2004
  • Content of chlorine in s쇼rene-DVB copolymer was decreased as crosslink increased and it is because as crosslink increased $1\%,\;2\%,\;5\%\;and\;10\%$ DVB content increased and crosslink density increased and cavity was reduced. Functional group of resin almost disappeared as C-C1 peak around $700cm^{-1}$ was substituted with 1-aza-12-C-4 macrocyclic ligand and new peak of C-N around $1020cm^{-1}$ appeared, so it was confirmed that styrene-DVB copolymer and ligand were compounded. As crosslink increased in the analysis of element contents, it resulted in the reduction of nitrogen content and it is because as crosslink increased, it led to the reduction of chlorine content in the process of substitution reaction and it affected macrocyclic ligand substituted. Form of functional synthetic resin showed distortion of its particles as macrocyclic ligand was introduced to styrene-DVB copolymer and hydrogen of ligand caused substitution with chlorine element of styrene molecule.

Kinetic Studies on the Ligand Substitution Reactions of Cyanocobalt(II) Complexes in Micellar Solutions (미셀용액에서 Cyanocobalt(II) 착물의 리간드치환 반응에 대한 속도론적 연구)

  • Ahn, Beom-Shu
    • Journal of the Korean Applied Science and Technology
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    • v.26 no.3
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    • pp.370-378
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    • 2009
  • Kinetic studies on the ligand substitution reactions of cyanocomplexes were performed in several micellar solutions. It showed the observed rate constants was found to be independent of the entering ligand concentration at high concentration of cyanopyridine and pyrazinecarboxylate. We could see also that in nonionic and anionic micellar solutions no influence of changes in the surfactant concentration on the observed rate constants was found. Taking into account the hydrophilic nature of the cobalt complex, the cobalt complex molecule was expected to be located in the aqueous phase of the micellar systems, where the reaction would take place. In cationic micellar solutions, a small increase in the observed rate constant was found when the cationic surfactant concentration increased. After reaching a maximum, the rate constant decreased on increasing surfactant concentration and subsequently it reached a plateau, where the observed rate constant was independent of changes in the surfactant concentration.

A Study on CO Substitution of Group 6 Metal Carbonyls by Using Phase Transfer Catalyst(2) (상이동촉매에 의한 GROUP 6 금속카르보닐의 CO 치환에 관한 연구(2) : 반응시간과 촉매량에 의한 영향)

  • Yang, Hyun-Soo;Park, Ha-Seon
    • Applied Chemistry for Engineering
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    • v.3 no.3
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    • pp.407-411
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    • 1992
  • The effects of phase transfer catalyst was studied on the substitution of CO ligand of $Mo(CO)_6$ [M=Cr, Mo, W] with two electron-pairs donating ligands, 2, 2'-bipyridine and 2, 2'-biquinoline. The change of product yield, $M(CO)_4(L)_2$, was discussed according to reaction time, mole composition of $M(CO)_6$, and type of ligand.

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Co-Electrodeposition of Bilirubin Oxidase with Redox Polymer through Ligand Substitution for Use as an Oxygen Reduction Cathode

  • Shin, Hyo-Sul;Kang, Chan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3118-3122
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    • 2010
  • The water soluble redox polymer, poly(N-vinylimidazole) complexed with Os(4,4'-dichloro-2,2'-bipyridine)$_2Cl]^+$ (PVI-[Os(dCl-bpy)$_2Cl]^+$), was electrodeposited on the surface of a glassy carbon electrode by applying cycles of alternating square wave potentials between 0.2 V (2 s) and 0.7 V (2 s) to the electrode in a solution containing the redox polymer. The coordinating anionic ligand, $Cl^-$ of the osmium complex, became labile in the reduced state of the complex and was substituted by the imidazole of the PVI chain. The ligand substitution reactions resulted in crosslinking between the PVI chains, which made the redox polymer water insoluble and caused it to be deposited on the electrode surface. The deposited film was still electrically conducting and the continuous electrodeposition of the redox polymer was possible. When cycles of square wave potentials were applied to the electrode in a solution of bilirubin oxidase and the redox polymer, the enzyme was co-electrodeposited with the redox polymer, because the enzymes could be bound to the metal complexes through the ligand exchange reactions. The electrode with the film of the PVI-[Os(dCl-bpy)$_2Cl]^+$ redox polymer and the co-electrodeposited bilirubin oxidase was employed for the reduction of $O_2$ and a large increase of the currents was observed due to the electrocatalytic $O_2$ reduction with a half wave potential at 0.42 V vs. Ag/AgCl.

Kinetics and Stereochemistry of CO Substitution Reactions of Half-Open Chromocene Carbonyls(Ⅲ): Reactions of $Cp^{*}(\eta^{5}-C_{5}H_{7})$CrCO and Phosphines

  • Jong-Jae Chung;Byung-Gill Roh;Yu-Chul Park
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.549-554
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    • 1993
  • The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.

Stereoselective Ligand Exchange Reaction of trans-dichlorocobalt(III) complex contained SS-epm and racemi propane-1,2-diamine (SS-epm이 배위된 trans-dichlorocobalt(III) 착물과 라세미 propane-1,2-diamine과의 입체선택적 리간드 치환반응)

  • Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.3 no.1
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    • pp.77-82
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    • 2000
  • The stereoselective ligand exchange reaction of trans-$[Co(SS-epm)Cl_2]^+$ and racemic propane-1,2-diamine (rac-pn) produces the complex that is identified as $[CO(N)_6]^{3+}$ type of $[Co(SS-epm)(pn)]^{3+}$ by absorption spectrum. It is conceivable that the reaction mechanism involves substitution and isomerization. The calculated and experimentally determined ratios of the complexed enantiomeric substrates at equilibrium were as follows: $[Co(SS-epm)(pn)]^{3+}$,calcd 32 % / 68 %, exptl 19 % / 81 % R-pn / S-pn. It has been shown that the employment of molecular mechanics calculations as a predictive tool may lead to the design of chiral complexes that may be applied to the separation of racemic mixtures of simple bidentate ligands.

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Cobalt(III) Complexes of 1,3-Diaminopropane-N,N'-di-α-(β-methyl)-pentanoic Acid

  • 함혜영;박영준;전무진
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.827-831
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    • 1997
  • A novel ONNO-type tetradentate ligand, 1,3-diaminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2apmp) and its cobalt(Ⅲ) complexes, [Co(apmp)X2]n+, (X=Cl-, NO2-, H2O, X2=CO32-, en, L-phenylalanine) have been synthesized. During the preparation of the dichloro cobalt(Ⅲ) complex of apmp, [Co(apmp)Cl2]-, the ligand has coordinated to the cobalt(Ⅲ) ion in a geometric selectivity to give only the uns-cis isomer and, during the substitution reaction between L-phenylalanine and [Co(apmp)Cl2]-, the L-phenylalanine has coordinated to the cobalt(Ⅲ) ion in a geometric selectivity to give only an uns-cis-meridional isomer. It is of interest that this is a rare case of the [Co(ONNO ligand)X2]n+-type complex preparations, which gives only an uns-cis isomer with geometric selectivity.

NMR Analysis of the Substitution of Titanium Tetraisopropoxide with Phenol and Carboxylic Acid

  • Choi, Jeong Chul;Hwang, Kwang-Jin
    • Journal of the Korean Magnetic Resonance Society
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    • v.21 no.4
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    • pp.135-138
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    • 2017
  • Titanium phenoxide and titanium carboxylate derivatives were prepared by ligand exchange of titanium tetraisopropoxide with the corresponding phenol and carboxylic acids. The substitution reactions were analyzed by NMR focused in the liberation of isopropylalcohol. The chemical shift of secondary proton of isopropyl group shifted to upfield after liberation; from 4.47 ppm at titanium-bound to 4.1~4.3 ppm at free alcohol state in $CDCl_3$. The substitution reaction of titanium tetraisopropoxide with carboxylic acid was applied to form dye-Ti complex for dye-sensitized solar cell.