• Title/Summary/Keyword: 금속 착물

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Studies on the Metal Complexes with the Tetradentate Schiff Base Ligand (네자리 Schiff Base 리간드의 금속착물에 관한 연구)

  • Chjo Ki Hyung;Oh Sang-Oh;Kim Chan-ho
    • Journal of the Korean Chemical Society
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    • v.18 no.3
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    • pp.194-201
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    • 1974
  • The tetradentate schiff base ligand, N,N'-bis(salicylaldehyde)-m-phenylenediimine has been prepared from salicylaldehyde and m-phenylenediamine by Duff-reaction. The schiff base ligand has been reacted with Cu(II), Ni(II), Co(II), and Zn(II) to form new complexes; Cu(II)$[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Ni(II)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O, Co(III)[C_{20}H_{14}O_2N_2]{\cdot}2H_2O and Zn(II)2[C_{20}H_{14}O_2N_2]{\cdot}4H_2O$. It seems to be that the Cu(II), Ni(II) and Co(II) complexes have hexacoordinated configuration with the schiff base and two molecules of water, while Zn(II) complex has tetracoordinated configuration with the schiff base and four molecules of water. The mole ratio of tetradentate schiff base ligand to Cu(II), Ni(II) and Co(II) are 1:1 but to Zn(II) is 1:2. These complexes have been identified by visible spectra, infrared spectra, T.G.A. and elemental analysis.

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Syntheses of New Nitrogen-Oxygen Multidentate Ligands and Their Stability Constants of Transition Metal(Ⅱ) Ions (새로운 질소-산소계 여러 자리 리간드의 합성 및 전이금속(Ⅱ)이온 착물의 안정도상수)

  • Kim, Sun Deuk;Jang, Ki Ho;Kim, Jun Kwang
    • Journal of the Korean Chemical Society
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    • v.42 no.5
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    • pp.539-548
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    • 1998
  • Multidentate N,O-containing ligands, such as N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED), N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT) and N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine (BHTP) were synthesized by reduction of the imine group of Bis(salicylidene)-ethylendiamine(BSED), Bis (salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylentriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) and Bis(salicylidene)-tetraethylenepentaamine(BSTP). Proton dissociation constants of the ligands and stability constants of transition metal(Ⅱ) ion complexes with BHED, BHPD, BHDT, BHTT, and BHTP were determined by potentiometic titration. The sequence of stability constants $(logK_{ML})$ of complex increases as BHED Zn(Ⅱ) which follows the Irving-Williams series.

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Complexes of Alkaline Earth Metals with Dibasic Organic Acids in Aqueous, Ethanol-Water and Acetone-Water Solutions (알칼리토류 금속과 2 염기 유기산 사이의 착물)

  • Sang Up ChoI;Chang Hwan Lee
    • Journal of the Korean Chemical Society
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    • v.17 no.6
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    • pp.416-423
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    • 1973
  • Formation of the complexes of alkaline earth metal ions with malonate and o-phthalate ions in aqueous, ethanol-water and acetone-water solutions (20% by volume) was studied at room temperature by the equilibrium ion exchange technique. This technique involved the measurements of distribution of radioactivity between cation exchange resin(Ion Exchange Resin CGC 241) and solution phases after the radioactive metal ions were equilibriated with the cation exchange resin in the presence of malonate or o-phthalate ions of varying concentrations. The pH of the solutions was controlled to 7.2~7.5, and the ionic strength of the solutions was kept at 0.10~0.11. The results of the present study indicated that the alkaline earth metal ions formed one-to-one complexes with the dibasic organic acids in all solvent systems examined. The present study showed that the relative stabilities of the complexes increased in the order: $Ba^{++}\;<\;Sr^{++}\;<\;Ca^{++}$ complexes. It was also observed that the relative tendency of the o-phthalate ion for the complex formation was somewhat greater than that of malonate ion in each solvent system. Furthermore, it was noted that the complexes were formed more readily in the mixed solvent than in the aqueous solution.

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Theoretical Study of the Conformation of Cis Carbene-Olefin Transition Matal Complexes (시스 카벤-올레핀 전이금속 착물들의 형태에 대한 이론적 연구)

  • Seong-Kyu Park;Ill-Doo Kim;Joon-Tae Kim;Chang-Jin Choi;Young-Gu Cheun
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.802-811
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    • 1992
  • The conformations of several carbene-olefin-transition metal complexes[$(CO)_4M$-(CHX)olefin] (X: $OCH_3,\;NHCH_3,\;SCH_3$, M: C, Mo, W) have been studied by means of Extend Huckel calculations. In the case of $d^6$ transition metal octahedral complexes, it is shown that the two main factors which determine the optimal conformation are metal-to-ligand back-donation and direct ligand-ligand interaction at the metal, but the ligand-ligand interaction dominates the situation for a metal that is coordinated to $\pi$ acceptor ligands and to $\pi$ donor group on the carbene. The relative amounts of both factors depend strongly on the electronic nature of the ligands at the metal. The greater electron donating ability of nitrogen stabilizes amino-substituted carbene complexes compared with their alkoxyl substituted analogues. This interaction is optimal when the $\pi$ systems of the carbene and olefin are coplanar. The introduction of the $\pi$ donor group on the carbene carbon increases also the importance of the ligand-ligand interaction.

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Stability Constants of Nitrogen-Oxygen Donor Macrocyclic Ligand-Metal Ion Complexes in Aqueous Solutions (질소-산소 주개 거대고리 화합물-금속착물의 수용액에서의 안정도상수)

  • Jeong Kim;Chang-Ju Yoon;Hyu-Bum Park;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.35 no.2
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    • pp.119-127
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    • 1991
  • The protonation and the metal ion complexation of 15 to 18 membered diaza crown ether such as 1,12-diaza-3, 4 : 9, 10-dibenzo-5, 8-dioxacyclopentadecane(NtnOenH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-hydroxy-5,9-dioxacyclohexadecane(NtnOtnH$_4$), 1,13-diaza-3,4 : 10,11-dibenzo-15-hydroxy-5,9-dioxacyclohexadecane(Ntn(OH)OtnH$_4$), 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdienH$_4$) and 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane(NtnOdienH$_4$) were studlied by potentiometry and NMR spectroscopy. The protonation constants were used to predict basicity of crown ethers. The sequence of the basicity was NenOdienH$_4$ < Ntn(OH)OtnH$_4$ < NtnOenH$_4$ < NtnOtnH$_4$ < NtnOdienH$_4$. Changes on the basicity were explained in terms of the effects of substituents and the degree of twistness of the macrocyclic ring. The sequence of the complex stabilities were Co(II) < Ni(II) < Cu(II) < Zn(II) for the transition metal complexes and Cd(II) < pb(II) < Hg(II) for the post-transition metal complexes. These changes on the stabilities were dependent on the basicity of the ligand and cavity size of the ring. For the heavy post-transiton metal complexes and Zn(Ⅱ) complex, the former factor was predominent and for the other transition metal complexes, the latter was affected on the stabilities. $^1$H and $^{13}$C-NMR studies for heavy post-transition metal complexes indicated that the nitrogen atom has greater affinity on metal ions than oxygen atom and the planarity of the rings was losed by the complexation with metal ions.

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Studies on the Complexation of a Nitrogen-Oxygen Donor Macrocyclic Ligand with Transition Metal Ions in Dioxane-Water Mixed Solvent (물-다이옥산 혼합용매에서 $N_2O_2$계 거대고리 리간드와 전이금속이온과의 착물형성에 관한 연구)

  • Moon-Hwan Cho;Sang-Chul Lee;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.503-508
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    • 1987
  • The protonation constants of 3,4 : 9,10-dibenzo-1,12-diaza-5,8-dioxacyclotetradecane $(NenOenH_4)$ and stability constants of its transition metal complexes have been determined by the potentiometric titration in 1 : 1 dioxane-water mixture with 0.1 ionic strength at $25^{\circ}C.$ For a given anion system, the stabilitv constants of the complexes are in the order of $Mn^{2+}<\;Co^{2+}\;< Ni^{2+}\;<\;Cu^{2+}\;>\;Zn^{2+}$, which accords with the Williams-Irving series.

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Synthesis and Properties of Polydentate Schiff Base Ligands having $N_nO_2$ (n=3~5) Donor Atoms and Bromine Substituent and their Transition Metal Complexes (여러자리 질소-산소계 시프염기 리간드와 전이금속착물의 합성 및 전기화학적 특성)

  • Kim, Sun-Deuk;Shin, Yun-Yeol;Park, Sung-Woo
    • Analytical Science and Technology
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    • v.11 no.6
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    • pp.440-447
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    • 1998
  • Polydentate Schiff base ligands 5-Br-BSDT(bis(5-bromosalicylaldehyde)diethylenetriamine) having $N_3O_2$ atoms, 5-Br-BSTT(bis(5-bromosalicylaldehyde)triethylenetetramine) having $N_3O_2$ atoms, 5-Br-BSTP(bis(5-bromosalicylaldehyde)tetraethylenepentamine) having $N_3O_2$ atoms were synthesized. Stability constants of the complexes between these ligands and the metal ions such as Cu(II), Ni(II) and Zn(II) were measured in DMSO by a polarographic method. It was observed that all metal(II) ions employed in this study formed 1 : 1 complexes with Schiff base ligands. Stability constants for the ligands were in the order of Cu(II)>Ni(II)>Zn(II), and for complex formation were in the order of 5-Br-BSTP>5-Br-BSTT>5-Br-BSDT according to the increasing in the number of donor atoms. Both enthalpy and entropy changes are obtained in negative valves. Exothermicity for the complex formation indicated tight binding between the ligands and metal ions. The negative entropy change would be related to the fact that solvent molecules are strongly interacting with the metal complexes.

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Synthesis, Chemical Characterization and Catalytic Activity of Transition Metal Complexes Having Imine Based Nitrogen Donor Ligand (이민에 기초한 질소주개 리간드의 전이금속 착물 합성, 화학적 특성 및 촉매활성)

  • Hussain, Raja Azadar;Badshah, Amin;Asma, Maliha
    • Journal of the Korean Chemical Society
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    • v.54 no.1
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    • pp.23-26
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    • 2010
  • A Schiff base ligand (Z)-N-((Z)-2-(sec-butylimino)-1,2-diphenylethylidene)butan-2-amine was synthesized by condensation of benzil with sec-butyl amine. Complexation of the ligand was carried out with first row transition elements, manganese(II) and nickel(II). Ligand and complexes were characterized by FTIR, elemental analysis and thermogravimetric analysis in solid state and by NMR ($^1H,\;^{13}C$) in solution form. Both the complexes demonstrate good catalytic activity for butadiene oligomerization under mild conditions with methylaluminoxane (MAO) as co-catalyst.

Photochemical Degradation of Polymers (고분자 물질의 광화학적 분해)

  • Sang Chul Shim;Hong Lim
    • Journal of the Korean Chemical Society
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    • v.19 no.6
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    • pp.454-462
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    • 1975
  • The photodegradation of polystyrene and polyethylene was studied utilizing several additives to promote photooxidation. Polymer films with small amount of additives were irradiated with ultraviolet lamps in Rayonet Photochemical Reactor. The progress of photodegradation was followed by measuring the intensities of carbonyl and hydroxyl stretching bands in infrared spectra as well as the viscosity changes. It was found that the increase of carbonyl or hydroxyl peaks was proportional to the decrease of the molecular weight of polymers under study. Iron(II, III) complexes of dithiocarbamate and their analogs showed good results.

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공액계 벤젠고리를 갖는 배위자에 의해 합성된 발광착체

  • Hwang, Hea-Eun;Kim, Dong-Ho;Bae, Jong-Bum;Ahn, Bong-Hee;Chung, Min-Chel
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2010.06a
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    • pp.151-151
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    • 2010
  • 본 연구에서는 배위자로 공액계 벤젠고리로 연결된 중심금속이 이리듐인 착물화합물과 합성하여 인광재료로서의 가능성을 실험하였다. 새로운 이리듐착물화합물의 화학적 구조를 알아보기 위해 $^1H$-NMR, $^{13}C$-NMR, UV-vis, spectrophotometer를 사용하였으며, 광 물리학적, 전기화학적 특성에 대한 측정은 spectrofluorometer, cyclic voltammetry를 통하여 측정하였다. 이리듐 단핵 및 이핵착체는 589~598nm의 영역에서 발광파장이 확인되었으며, DMSO[$5{\times}10^{-5}$]용액에서 양자효율이 단핵 착물화합물의 경우 0.1, 이핵착물화합물의 경우 0.13으로 나타났다. 이핵 이리듐착물화합물의 전기화학적 특성은 energy gap은 2.45eV, optical band gap은 2.58eV로 계산되었다.

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