• Title/Summary/Keyword: 전이금속 착물

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X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides (α-케토안정화된 일리드화 인의 수은(II) 및 은(I) 착물에 대한 X-선 및 분광학적 연구)

  • Karami, K.;Buyukgungor, O.;Dalvand, H.
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.38-45
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    • 2011
  • The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.

Synthesis of Tridentate Poly-amine Ligands and Determination of Stability Constants of Transition Metal Complexes (세자리 폴리아민리간드의 합성과 양성자 해리상수 및 전이금속과의 착물 안정도상수의 결정)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Ko, Moon-Soo
    • Analytical Science and Technology
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    • v.15 no.2
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    • pp.135-141
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    • 2002
  • The new tridentate poly-amine ligands, N,N-Bis(2-amino-ethyl)-methyl amine${\cdot}$2HBr (BAMA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-ethylamine${\cdot}$2HBr (BAEA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-propylamine${\cdot}$2HBr (BAPA${\cdot}$2HBr) and N,N-Bis(2-amino-ethyl)-butylamine${\cdot}$2HBr (BABA${\cdot}$2HBr) were synthesized as their dihydrobromic-salt and characterized by EA, IR, NMR and Mass spectroscopy. The protonation constants of the ligands and stability constants of transition metal(II) complexes were determined in aqueous solutions by potentiometry and compared with diethylenetriamine. Stability constants for transition metal complexes of ligands are in the order of BAMA < BAEA < BAPA > BABA. The larger value of stability constants of BAPA compared to these BABA, may be attributed to the more distorted structure of the complex due to the increased steric crowding caused by the presence of the bulky N-butyl group.

Synthesis and Characterization of Metal Complex Oxo Vanadium(Ⅳ) Complexes with Derivatives of Salicylaldoximes (옥심계 금속착물의 합성과 그 물성에 관한 연구 치환 살리실알데히드옥심의 바나듐(Ⅳ) 착물(1))

  • Lee, Kwang;Lee, Won Sik
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.611-616
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    • 1995
  • Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

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The Stability Constant of Transition and Lanthanide Metal Ions Complexes with 15 Membered Macrocyclic Azacrown Ligands (거대고리 아자크라운화합물과 전이금속 및 란탄족금속이온의 착물의 안정도)

  • Hong, Choon-Pyo;Choi, Yong-Gu;Choppin, G.R.
    • Journal of the Korean Chemical Society
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    • v.48 no.6
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    • pp.577-582
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    • 2004
  • The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

Synthesis, Characterization and Biological Activity of Some Complexes of Some New Amino Acid Derivatives N-[(Benzoyl amino)-Thioxomethyl]-Amino Acid(HL) (새로운 아미노산 유도체인 N-[(Benzoyl amino)-Thioxomethyl]-Amino Acid(HL)의 착물 합성, 특성규명 및 생물학적 활성)

  • Al-Mudhaffar, Dhafir M.H.;Al-Edani, Dawood S.;Dawood, Suma M.
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.506-514
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    • 2010
  • A new series of ligands N-[(benzoylamino)-thioxomethyl]-amino acid (HL) were synthesized by reaction of benzoylisothiocyanate with various amino acids namely aspartic acid [BATA] (1), glutamic acid [BATG] (2), methionine [BATM] (3), leucine [BATL] (4), and tryptophan [BATT] (5). The ligands were characterized by elemental analysis, IR and NMR spectra. Some transition metal complexes ($ML_2$) for these ligands (6-8) were prepared; [M=Cu(II), Co(II), or Ni(II)], and characterized by elemental analysis, IR and $^1H$ NMR spectra. Antibacterial study showed that all the ligands have no antibacterial activity, whereas ($ML_2$) complexes; [M = Cu(II), Co(II), or Ni(II)] have antibacterial activity towards (Gram -ive) Escherichia (NCTC5933) and (Gram +ive) Staphylococcus (NCTC6571) and have no toxicity on (BALB/C) Albino mice.

[살렌-크롬(III)]·Cl 착물을 단일 촉매로 한 고리형 카보네이트와 폴리카보네이트가 생성되는 반응 경로 제시

  • Park, Hyeon-U;Kim, Yeon-Jun;Baek, Gyeong-Yeop;Kim, U-Yeon
    • Proceeding of EDISON Challenge
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    • 2016.03a
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    • pp.113-115
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    • 2016
  • 온실가스의 주범을 친환경적으로 활용한다는 측면과 carbon source를 영구적으로 저렴한 비용으로 공급할 수 있다는 경제적 측면에서 CO2를 활용한 고부가가치 화학물질의 합성이 최근에 주목 받고 있다. 본 연구에서는 살렌(salen)-전이금속 착물을 단일 촉매로 사용한 모델 시스템을 통해 고부가가치 소비재의 주된 원료인 고리형 카보네이트 (cyclic carbonate)와 폴리카보네이트 (polycarbonate)가 생성되는 반응경로를 규명하였으며, 이들의 활성화 에너지를 조절함으로써 생성물을 선택적으로 합성할 수 있다는 이론적 근거를 제시하였다.

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Calculation of the Dipole Moments for Transition Metal Complexes by Valence Bond Method (I). Calculation of the Dipole Moments for Octahedral $[M(III)O_3S_3]$ Type Complexes [M(III) = V(III), Cr(III), Mn(III), Fe(III), Co(III), Ru(III), Rh(III) and Os(III)] (원자가 결합법에 의한 전이원소 착물에 대한 쌍극자모멘트의 계산 (제1보). 팔면체 $[M(III)O_3S_3]$ 형태 착물의 쌍극자모멘트의 계산 [M(III) = V(III), Cr(III), Mn(III), Fe(III), Co(III), Ru(III), Rh(III) 및 Os(III)])

  • Sangwoon Ahn;Jeoung Soo Ko
    • Journal of the Korean Chemical Society
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    • v.23 no.4
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    • pp.198-205
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    • 1979
  • A valence bond method of calculation of the dipole moments for octahedral $(M(III)0_3S_3)$ type complexes are developed, using $d^2sp^3 $hybrid orbitals of the central metal ions and the single basis set orbital of ligands. (M (III) =V (III), Cr (III), Mn (III), Fe (III), Co (III), Ru (III), Rh (III) and OS (III)). In this method the mixing coefficient of the valence basis sets for the central metal ion with the appropriate ligand orbitals is not required to be the same, differently from the molecular orbital method. The valence bond method is much more easier to calculate the dipole moments for octahedral complexes than the approximate molecular orbital method and the calculated results are also in the range of the experimental vaues.

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Studies on the Synthesis and Structure of Macrocyclic Complexes for Transition Metals. (Part 1) Effects of Stability Constant on the Co-formation of Mixed Chelates (EDTA and IMDA) with Lanthanon (La, Nd, Gd, Ho, Yb) (전이금속 착물들의 합성 및 결정구조 연구 (제 1 보) EDTA 와 IMDA 복합 킬레이트가 란탄족 원소들 (La, Nd, Gd, Ho, Yb)의 안정도 상수에 미치는 영향)

  • Young-Gu Ha;E. Y. Kim;Q. Won Choi;Hasuck Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.434-443
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    • 1987
  • The formation constants of the complexes between Ln-EDTA 1 : 1 complex and IMDA have been investigated by a potentiometric titration method at 20.0${\pm}$0.2 degree C and ${\mu}$ = 0.1 (KNO$_3$). Unusually large stability in Ln(EDTA) mixed ligand complexes was found. Trends in the formation constants vs. atomic number of the lanthanide metals were discussed on the basis of coordination number and ionic radius of the metals.

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Complexation of Polyelectroyte-Metal(II) Ion. III. The Complex Formation of Iron(II), Cobalt(II), Nickel(II) and Copper(II) with Branched Poly(ethylene imine) (BPEI) in Aqueous Solution (Polyelectrolyte-Metal(II) 이온의 착물화 (제 3 보). Iron(II), Cobalt(II) Nickel(II) 및 Copper(II)와 Branched Poly(ethylene imine) (BPEI)간의 착물생성)

  • Dong Soo Kim;Tae Sub Cho
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.456-464
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    • 1986
  • The complex formation of branched poly(ethylene imine) (BPEI) with bivalent transition metal ions, such as Fe(II), Co(II), Ni(II) and Cu(II), have been investigated in terms of visible absorption and pH titration methods in an aqueous solution in 0.1M KCl at 30${\circ}$. The stability constants for M(II)-BPEI complexes was calculated with the modified Bjerrum method. The formation curves of M(II)-BPEI complexes showed that Fe(II), Co(II), Ni(II) and Cu(II) ions formed coordination compounds with four, two, two, and two ethylene imine group, respectively. In the case of Cu(II)-BPEI complex at pH 3.4 ∼ 3.8, ${\lambda}_{max}$ was shifted to the red region with a decrease in the acidity. The overall stability constants (log $K_2$) increased as the following order, Co(II) < Cu(II) < Ni(II) < Fe(II).

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Synthesis of New N2O Tridentate Ligands and Their Stability Constants of Transition Metal Complexes (새로운 N2O계 세 자리 리간드의 합성과 전이금속 착물 안정도상수)

  • Kim, Sun-Deuk;Park, Young-Sik
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.569-577
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    • 2003
  • Ligands, Br-PEMP, Cl-PEMP and $CH_3O-PEMP$ having Br, Cl and $CH_3O$ substituents at 5-position of the $N_2O$ tridentate ligand, 2-[(2-pyridine-2-ethylamio)-methyl]-phenol (H-PEMP) containing pyridine and phenol were synthesized. Another ligand, Naph-PEMP having pyridine and 2-hydroxy-1-naphthalene was also synthesized. The ligands were characterized using elemental analysis, UV-visible, IR, $^1H\;NMR\;and\;^{13}C$ NMR spectroscopy and mass analysis. The potentiometric titration study in aqueous solution revealed that the proton dissociation of the ligands occurred in three steps and the order of overall proton dissociation constants (log${\beta}$) was $CH_3O-PEMP$ > Naph-PEMP > H-PEMP > Cl-PEMP > Br-PEMP. The order of stability constants (logML and log$ML_2$) of their transition metal complexes was Co(II) < Ni(II) < Cu(II) > Zn(II). The order in their stability constants values of each transition metal complex agreed well with that in overall proton dissociation constant value of the ligands.