• Title/Summary/Keyword: 전이금속 착물

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The Complex Formation of Fe(III)-Salicylic acid (Fe(III)-Salicylic acid의 착물 형성에 관한 연구)

  • Cha, Ki-Won;Park, Kwang-Won
    • Analytical Science and Technology
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    • v.8 no.3
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    • pp.305-311
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    • 1995
  • The stability constant of the complex between salicylic acid($H_2A$) and Fe(III) ion has been determined using UV-Vis absorption spectrometry and pH titration method in O.1M $KNO_3$ aqueous solution at $20^{\circ}C$ and compared with reference value, $logK_f=16.48$. The $pK_{a1}$ and $pK_{a2}$ of $H_2A$ are $2.92{\pm}0.08$ and $12.90{\pm}0.13$, respectively and the $logK_f$ of 1:1 complex Fe(III)-$H_2A$ system is $11.88{\pm}0.12$ at $20^{\circ}C$.

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Synthesis and Characterization of New Transition Metal Complexes of Schiff-base Derived from 2-Aminopyrimidine and 2,4-Dihydroxybenzaldehyde and Its Applications in Corrosion Inhibition (2-Aminopyrimidine 및 2,4-Dihydoxybenzaldehyde 치환체인 Schiff-염기의 전이금속 착물에 대한 합성 및 특성 그리고 부식방지에의 응용)

  • Ouf, Abd El-Fatah M.;Ali, Mayada S.;Soliman, Mamdouh S.;El-Defrawy, Ahmed M.;Mostafa, Sahar I.
    • Journal of the Korean Chemical Society
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    • v.54 no.4
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    • pp.402-410
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    • 2010
  • New complexes cis-[$Mo_2O_5(Hapdhba)_2$], trans-[$UO_2(Hapdhba)_2$], [Pd(Hapdhba)Cl($H_2O$)], [Pd(bpy)(Hapdhba)]Cl, [Ag(bpy)(Hapdhba)], [$Ru(Hapdhba)_2(H_2O)_2$], [$Rh(Hapdhba)_2Cl(H_2O)$] and [Au(Hapdhba)$Cl_2$] are reported, where $H_2$apdhba is the Schiff-base derived from 2-aminopyrimidine and 2,4-dihydroxy benzaldehyde. The complexes were characterized by IR, electronic, $^1H$ NMR and mass spectra, conductivity, magnetic and thermal measurements. The inhibitive effect of $H_2$apdhba for the corrosion of copper in 0.5 M HCl was also determined by potentiodynamic polarization measurements.

Synthesis of Schiff-Base Ligands and Determination of Stability Constants of Their Transition Metal(II) Complexes (질소-산소계 시프염기 리간드의 합성과 전이금속(II) 착물의 안정도상수결정)

  • Kim, Seon Deok;Song, Chan Ik;Kim, Jun Gwang;Kim, Jeong Seong
    • Journal of Environmental Science International
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    • v.13 no.9
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    • pp.835-843
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    • 2004
  • N,N-bis(2-salicylaldehyde)dipropylenetriamine(5- Hsaldipn), N,N-bis( 5-bromosalicyl-aldehyde) dipropylenetriamine (5-Brsaldipn), N,N-bis(5-chlorosalicy laldehyde )dipropylene-triamine(5-Clsaldipn), N,N-bis(2-hydroxy- $5-methoxy-benzaldehyde)dipropylenetriamine(5-OCH_3saldipn)$ and N,N-bis (2-hydroxy-5-nitrobenzaldehyde)dipropylenetriamine $(5-NO_2saldipn)$ were synthesized and characterized by elemental analysis, infrared spectrometry, NMR spectrometry and mass spectrometry. Their proton dissociation constants were determined in 70% dioxane/30% water solution by potentiometric. Stability constants of the complexes between these ligands and the metal ions such as Cu(II), Ni(II) and Zn(II) were measured in dimethyl sulfoxide by a polarographic method. Stability constants for the ligands were in the order of $5-OCH_3$ > 5-H > 5-Br > 5-Cl > $5-NO_2$ saldipn. Enthalpy and entropy changes were obtained in negative values.

Stability Constants for Transition Metal ions of Hexadentate $N_6$ Ligands Containing Two Pyridyl Groups (피리딘을 포함하는 여섯자리 $N_6$ 리간드와 전이금속 이온 착물의 안정도상수)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Park, Yoon-Yul
    • Analytical Science and Technology
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    • v.12 no.5
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    • pp.397-402
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    • 1999
  • The open-chain hexadentate $N_6$, ligand containing two pyridyl groups, 1,15-bis(2-pyridyl)-2,6,10,14-tetraazapentadecane (bpyped) has been synthesized as its tetrahydroehloride salt and characterized by EA, IR, NMR, and Mass. Its proton dissociation constants($logK{^n}_H$) and stability constants ($log\;K_{ML}$) for Co(II), Ni(II), Cu(II) and Zn(II) ions were determined at $25^{\circ}C$ and ionic strength 0.10 M($KNO_3$) in aqueous solution by potentiometry and compared with those or analogous $N_6$ ligands contain one or two propylenic spacers, which make six-membered chelate rings, between the aliphatic nitrogen atoms.

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Kinetics and Mechanism for Aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3^-$, NO$_2$, NCS$^-$, H$_2$O} in Hg$^{2+}$ Aqueous Solution ($Hg^{2+}$ 수용액 내에서 cis-[Co(en)$_2$YCl]$^{r+}$ (Y = $NH_3$, NO$_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도와 반응메카니즘)

  • Byung-Kak Park;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.476-482
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    • 1988
  • Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

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Kinetic Studies of Reaction of Transion Metal Ion with Macrocyclic Ligands. Containing Nitrogen and Oxygen Donor Atoms (전이금속 이온과 Macrocyclic Ligand 사이의 반응에 관한 속도론적 연구 질소원자와 산소원자를 포함하는 거대고리 리간드를 중심으로)

  • Kim Jin-Ho;Cho Moon-Hwan;Hyeoun Dong-Ho;Park Hyu-Bum;Kim Si-Joong;Lee Ihn-Chong
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.418-423
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    • 1990
  • The protonation constants for the macrocyclic ligands 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloeicosane (NdienOdienH$_4$), 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa cycloheptadecane (NdienOenH$_4$), and 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloheptadecane (NenOdienH4) have been determined by the potentiometry in aqueous solutions (25$^{\circ}C$, I = 0.1, KNO$_3$). The stability constants for complexes formed in the aqueous solution (25$^{\circ}C$, I = 0.1, KNO$_3$) between the above ligands and the metal ions (Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)) have been measured by potentiometry. The rate of the ligand substitution reaction was measured spectrophotometrically by the addition of aqueous solutions of ethylenediamine to the solution of the complex. From the study of the temperature effect on the rate constant (k$_{obs}$), activation parameters (E$_a$,${\{Delta}H^{\neq}$, and ${\{Delta}S^{\neq}$) have been determined. The possible mechanism for the substitution reaction is proposed.

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Structure and Chemical Reactivity of the Transition Metal Complexes (I). Synthesis and Geometrical Isomerism of the Ethylenediamine-triacetatocobalt (III) Complexes with Ammine or Diamines (전이금속착물의 구조와 그 반응성 (I). 암민류를 포함하는 Ethylenediamine-triacetatocobalt (III) 착물의 합성과 기하이성질현상)

  • Dong-Jin Lee;Bong-Gon Kim;Myung-Ki Doh
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.516-521
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    • 1985
  • Ethylenediamine-triacetatocobalt (III) complexes with an ammine, an ethylene-diamine, and a trimethylenediamine as the unidentate ligand were prepared, and were isolated as only one isomer for each case by the Dowex 50W-X8, cation exchange resin in $H^+$ form. The geometrical isomer of these complexes have been assigned cis-equatorial form in the three possible geometrical isomers from the elemental analysis, pH titration, IR, NMR, and electronic absorption spectrum. It was found that $[CoN_3O_3]$ system of the meridional form with multidentate ligand have the first absorption band of the largely splitting pattern, and that the diamines (ethylenediamine, trimethylenediamine) have coordinated to the central cobalt (III) ion as a unidentate ligand.

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Complex Formation of 1,15-Diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane with Some Transition Metal Ions (전이금속이온과 1,15-Diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane과의 착물형성)

  • Cheul-Gyu Chang;Young-Kook Shin;Si-Joong Kim
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.526-531
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    • 1986
  • The stability constants of 1,15-diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdien H$_4$, L) with transition metal ions such as $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ have been determined by potentiometry in 95% methanol solution at 25$^{\circ}$C. The complex formation of the NenOdien $_4$ with the transition metal ions depends on the basicity of the donor atoms. The order of complex stability was Co(II) < Ni(II) < Cu(II) > Zn(II). The geometries of the complexes in solid state were discussed by visible-near infrared and infrared spectrophotometry, elemental analysis and electro-conductivity. The results suggest that the geometries of the solid complexes are octahedral for $[CoL_2(OH_2)Cl]Cl{\cdot}2H_2O$, $[NiL_2(OH_2)Cl]Cl{\cdot}2H_2O$, and $[ZnLCl_2]{\cdot}\frac{1}{2}H_2O$ and square pyramidal for [CuLCl]Cl, respectively.

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Electronic Structure and Chemical Reactivity of Transition Metal Complexes (Part 16). A Spectroscopic Study on the Electronic Structure of cis-[Cr(cyclam)$Cl_2$]Cl (전이금속 착물의 전자 구조 및 화학적 반응성 (제 16 보). cis-[Cr(cyclam)$Cl_2$]Cl의 전자 구조에 관한 분광학적 연구)

  • Choi, Jong-Ha
    • Journal of the Korean Chemical Society
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    • v.39 no.7
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    • pp.501-507
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    • 1995
  • The electronic structure of cis-$[Cr(cyclam)Cl_2]Cl$ has been investigated by the emission and excitation spectroscopy at 77K, and infrared and visible spectroscopy at room temperature. The ten electronic transitions due to spin-allowed and spin-forbidden are assigned. The zero-phonon line in the excitation spectrum splits into two components by $139\;cm^{-1}$, and it can be reproduced by modern ligand field theory. According to the results of ligand field analysis, we can confirm that nitrogen atoms of the cyclam ligand have a strong ${\sigma}$-donor character, but chloride ligand has weak ${\sigma}-$ and ${\pi}-$donor properties toward chromium(III) ion.

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Synthesis and Structural Characterization of Transition Metal Complex with N,N'-bis-[2(S) -pyrrolidinylmethyl]phenylene-1,2-diamine (N,N'-Bis[2(S)-2-pyrrolidinylmethyl]phenylene-1,2-diamine를 배위하는 전이금속 착물의 합성 및 구조적 특성)

  • Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.1 no.1
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    • pp.43-49
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    • 1998
  • The SS-phpm 4HCl(N,N'-bis-[2(S)-pyrrolidinylmethyl]phenylene-l,2-diamine-4-Hydrochloride) ligand having stereospecificity has been prepared and reacted with trans-[$Co(pyridine)_4Cl_2]$Cl. The resultants are purple crystals, which are identified to be ${\Delta}$-cis-${\beta}$-[$Co(SS-phpm)Cl_2$]Cl by elemental analysis and UV/Vis- and CD-absorption spectra, The conformation of SS-phpm in ${\Delta}$-cis-${\beta}$ complex is ${\delta}$ ${\varepsilon}$ ${\lambda}$ (SSSS) for each of the five-membered chelated ring. Futhermore, according to orientation of secondary amine, total strain energy on each isomers was calculated by molecular mechanics(MM) to verify structural characterization and spectral data. As the result, the most stabilized isomer was ${\Delta}$-cis-${\beta}$(SSSS). The value of total strain energy(U) of ${\Delta}$-cis-${\beta}$(SSSS) isomer was 63.21 kcal/mol, respectively.

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