• Title/Summary/Keyword: Ligand-exchange reaction

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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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Studies on Reactions of a Nickel Complex of a New Completely Conjugated Macrocyclic Ligand

  • Park, Young-Ae W.;Oh, Soon-Song
    • Bulletin of the Korean Chemical Society
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    • v.8 no.6
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    • pp.476-479
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    • 1987
  • The macrocyclic nickel complex of the molecular formula[Ni($C_{32}H_{26}N_4$)] has been synthesized from the template condensation reaction between 1-benzoylacetone and o-phenylenediamine in the presence of nickel acetate. Protonation and deuterium exchange reactions of the demetallated macrocyclic ligand and the nickel complex have been carried out. The infrared, electronic and proton magnetic resonance spectral data of both compounds are compared and discussed; protonation of the macrocyclic ligand take place at the nitrogen atoms and all the amine protons undergo very rapid deuterium exchange while the methine protons undergo very slow exchange. On the other hand, protonation of the nickel complex occurs at the nitrogen atoms and only amine protons undergo rapid deuterium exchange. Protonation and deprotonation of the nickel complexes proceed reversibly.

Studies on the Heavy Metal Removal Characteristics of $FeS_(S)$ in the Presence of Organic Ligand (유기 리간드 존재하에서 $FeS_{(S)}$의 중금속 제거 특성 연구)

  • 박상원;박병주
    • Journal of Environmental Science International
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    • v.8 no.3
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    • pp.411-417
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    • 1999
  • The interfacial chemical behavior, lattice exchange and dissolution, of $FeS_{(S)}$ as one of the important sulfide minerals was studied. Emphases were made on the surface characterization of hydrous $FeS_{(S)}$, the lattice exchange of Cu(II) and $FeS_{(S)}$, and its effect on the dissolution of $FeS_{(S)}$, and also affect some organic ligands on that of both Cu(II) and $FeS_{(S)}$. Cu(II) which has lower sulfide solubility in water than $FeS_{(S)}$ undergoes the lattice exchange reaction when Cu(II) ion contacts $FeS_{(S)}$ in the aqueous phase. For heavy metals which have higher sulfide solubilities in water than $FeS_{(S)}$, these metal ions were adsorbed on the surface of $FeS_{(S)}$. Such a reaction was interpreted by the solid solution formation theory. Phthalic acid(a weak chelate agent) and EDTA(a strong chelate agent) were used to demonstrate the effect of organic lignads on the lattice exchange reaction between Cu(II) and $FeS_{(S)}$. The $pH_{zpc}$ of $FeS_{(S)}$ is 7 and the effect of ionic strength is not showed. It can be expected that phthalic acid has little effect on the lattice exchange reaction between Cu(II) and $FeS_{(S)}$. whereas EDTA has very decreased the removal of Cu(II) and $FeS_{(S)}$. This study shows that stability of sulfide sediments was predicted by its solubility. The pH control of the alkaline-neutralization process to treat heavy metal in wastewater treatment process did not needed. Thereby, it was regarded as an optimal process which could apply to examine a long term stability of marshland closely in the treatment of heavy metal in wastewater released from a disussed mine.

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Study on the Adsorption Behavior of FeS in Anaerobic Conditions (혐기성 조건에서 FeS의 흡착 거동 연구)

  • 김정배
    • Journal of Environmental Science International
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    • v.6 no.5
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    • pp.505-512
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    • 1997
  • The Interfacial characteristics between various heavy metals and hydrous FeS were investigated. Heavy metals which have lower sulfide solubilities than FeS undergoes the lecttice exchange reaction when these metal tons contact FeS In the aqueous phase. For heavy metals which have higher suede solubilities than FeS, these metal ions adsorb on the surface of FeS. Such characteristic reactions were interpreted by the soled solution formation theory. The presence of ligand such as EDTA reduced largely metal removal efficiency due to formation of metal-ligand complex In the solution. In an attempt to elucidate the Interfacial characteristics, zeta potential of the hydrous FeS In the absence and In the presence of various metal loons were measured and analyzed.

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Optical Resolution of Dansyl Amino Acids with Addition of Benzyl-L-Hydroxyproline Copper(II) Chelate by High Performance Liquid Chromatography

  • Sun Haing Lee;Tae Sub Oh;Sang Hyun Bak
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.491-495
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    • 1989
  • Resolution of enantiomers of DNS-amino acids has been achieved by a reversed phase liquid chromatography with an addition of a copper(Ⅱ) complex of N-benzyl-L-hydroxyproline to the mobile phase. N-Benzyl-L-hydroxyproline was prepared and used as a chiral ligand of copper(Ⅱ) chelate for the optical resolution. The pH and the concentration of copper(Ⅱ) chelate, organic solvent, and buffer agent in the mobile phase all affect the optical resolutions of dansyl amino acids. The elution orders between D and L-DNS-amino acids were different depending on the structure of the side chain of the amino acids. The retention mechanism for the chiral separation of the dansyl amino acids can be illustrated by the equilibrium of ligand exchange and by hydrophobic interaction with $C_{18}$ stationary phase. The chiral separation can be illustrated with cis and trans effect of the ligand exchange reaction.

Synthesis of Highly Dispersed Pd Nanocatalysts Through Control of Organic Ligands and Their Electrochemical Properties for Oxygen Reduction Reaction in Anion Exchange Membrane Fuel Cells (유기 리간드 제어를 통한 고분산 팔라듐 나노 촉매의 합성 및 음이온교환막 연료전지를 위한 산소 환원 반응 특성 분석)

  • Sung, Hukwang;Sharma, Monika;Jang, Jeonghee;Jung, Namgee
    • Korean Journal of Materials Research
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    • v.28 no.11
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    • pp.633-639
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    • 2018
  • In anion exchange membrane fuel cells, Pd nanoparticles are extensively studied as promising non-Pt catalysts due to their electronic structure similar to Pt. In this study, to fabricate Pd nanoparticles well dispersed on carbon support materials, we propose a synthetic strategy using mixed organic ligands with different chemical structures and functions. Simultaneously to control the Pd particle size and dispersion, a ligand mixture composed of oleylamine(OA) and trioctylphosphine(TOP) is utilized during thermal decomposition of Pd precursors. In the ligand mixture, OA serves mainly as a reducing agent rather than a stabilizer since TOP, which has a bulky structure, more strongly interacts with the Pd metal surface as a stabilizer compared to OA. The specific roles of OA and TOP in the Pd nanoparticle synthesis are studied according to the mixture composition, and the oxygen reduction reaction(ORR) activity and durability of highly-dispersed Pd nanocatalysts with different particles sizes are investigated. The results of this study confirm that the Pd nanocatalyst with large particles has high durability compared to the nanocatalyst with small Pd nanoparticles during the accelerated degradation tests although they initially indicated similar ORR performance.

Studies on the Metal-Exchange Reaction of Tetrahedral Cu(II) Complex with Mercuric Ion and Mercury Metal (정사면체 구조를 갖는 Cu(II) 착물과 수은(II) 및 수은(0)과의 금속 교환반응 연구)

  • Young Tae Gong;Sung Nak Choi;Yoon-Bo Shim
    • 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.

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InP Quantum Dot - Organosilicon Nanocomposites

  • Dung, Mai Xuan;Mohapatra, Priyaranjan;Choi, Jin-Kyu;Kim, Jin-Hyeok;Jeong, So-Hee;Jeong, Hyun-Dam
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.191-191
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    • 2012
  • InP quantum dot (QD) - organosilicon nanocomposites were synthesized and their photoluminescence quenching was mainly investigated because of their applicability to white LEDs (light emitting diodes). The as-synthesized InP QDs which were capped with myristic acid (MA) were incompatible with typical silicone encapsulants. Post ligand exchange the MA with a new ligand, 3-aminopropyldimethylsilane (APDMS), resulted in soluble InP QDs bearing Si-H groups on their surface (InP-APDMS) which allow embedding the QDs into vinyl-functionalized silicones through direct chemical bonding, overcoming the phase separation problem. However, the ligand exchange from MA to APDMS caused a significant decrease in the photoluminescent efficiency which is interpreted by ligand induced surface corrosion relying on theoretical calculations. The InP-APDMS QDs were cross-linked by 1,4-divinyltetramethylsilylethane (DVMSE) molecules via hydrosilylation reaction. As the InP-organosilicon nanocomposite grew, its UV-vis absorbance was increased and at the same time, the PL spectrum was red-shifted and, very interestingly, the PL was quenched gradually. Three PL quenching mechanisms are regarded as strong candidates for the PL quenching of the QD nano-composites, namely the scattering effect, Forster resonance energy transfer (FRET) and cross-linker tension preventing the QD's surface relaxation.

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Thermal Atomic Layer Etching of the Thin Films: A Review (열 원자층 식각법을 이용한 박막 재료 식각 연구)

  • Hyeonhui Jo;Seo Hyun Lee;Eun Seo Youn;Ji Eun Seo;Jin Woo Lee;Dong Hoon Han;Seo Ah Nam;Jeong Hwan Han
    • Journal of Powder Materials
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    • v.30 no.1
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    • pp.53-64
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    • 2023
  • Atomic layer etching (ALE) is a promising technique with atomic-level thickness controllability and high selectivity based on self-limiting surface reactions. ALE is performed by sequential exposure of the film surface to reactants, which results in surface modification and release of volatile species. Among the various ALE methods, thermal ALE involves a thermally activated reaction by employing gas species to release the modified surface without using energetic species, such as accelerated ions and neutral beams. In this study, the basic principle and surface reaction mechanisms of thermal ALE?processes, including "fluorination-ligand exchange reaction", "conversion-etch reaction", "conversion-fluorination reaction", "oxidation-fluorination reaction", "oxidation-ligand exchange reaction", and "oxidation-conversion-fluorination reaction" are described. In addition, the reported thermal ALE processes for the removal of various oxides, metals, and nitrides are presented.

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.