• Title/Summary/Keyword: Tridentate ligands

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Synthesis of New N,N,O Tridentate Ligands and Determination of Stability Constants of Transition Metal Complexes by Potentiometry (새로운 N,N,O계 세 자리 리간드의 합성과 전위차적정법에 의한 전이금속 착물의 안정도상수의 결정)

  • Kim, Sun-Deuk;Lee, Do-Hyub
    • Journal of Environmental Science International
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    • v.15 no.8
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    • pp.799-809
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    • 2006
  • Hydrobromic acid salts of new N, N, O tridentate ligands containing phenol, 2-[(2-Methylamino- ethyl- amino)-methyl]-phenol(H-MMP. 2HBr), 5-Bromo-2-[(2-Methylamino-ethylamino)-methyl]-phenol (Br- MMP. 2HBr), 5-Chloro-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Cl-MMP. 2HBr), 5-Methyl-2-[(2-Methylamino-ethylamino)-methyl]-phenol(Me-MMP. 2HBr), 5-Methoxy-2-I(2-Methylamino-ethylamino)- methyl]-phenol(MeO- MMP. 2HBr) and. 1-[(2-Methylamino-ethylamino)- methyl]-naphthalen-2-ol(Nap- MMP. 2HBr) were synthesized. The synthesized ligands were confirmed by C. H. N. atomic analysis, UV-visible and IR spectroscopies, $^1$H NMR, $^{13}$C NMR and mass analysis. The potentiometry study revealed that the proton dissociation constants(logK$_n^H$) of the synthesized ligands and stability constants (logK$_{ML}$, logK$_{LM2}$) of transition metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions occurred in three steps and the order of the calculated overall proton dissociation constants(log$\beta_p$) and stability constants (logK$_{ML}$) of ligands was Br-MMP. 2HBr < Cl-MMP 2HBr < H-MMP. 2HBr < Nap-MMP. 2HBr < Me-MMP. 2HBr < MeO-MMP. 2HBr. The order showed a similar trend to that of Hammett substituent constants($\delta_p$). The synthesized ligands usually form 2:1(ML$_2$) complexes with transition metal ions. The order of the stability constants of each transition metal ions was Co(II) < Ni(II) < Cu(II) ;> Zn(II) ;> Cd(II) ;> Pb(II).

New Tridentate Ligands with Mixed Donor Atoms for Cu-Based Atom Transfer Radical Polymerization

  • Cho, Hong-Youl;Han, Byung-Hui;Kim, Il;Paik, Hyun-Jong
    • Macromolecular Research
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    • v.14 no.5
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    • pp.539-544
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    • 2006
  • 2-Furancarboxaldehyde-2-pyridinylhydrazone (FPH) and 5-methyl-2-furancarboxaldehyde-2-pyridinylhydrazone (MFPH) were synthesized and used as tridentate ligands of copper (I) bromide for the atom transfer radical polymerization of methyl methacrylate (MMA) and styrene. The polymerization of methyl methacrylate achieved high conversion and yielded polymers with a good control of molecular weight and low polydispersity (PDI=1.33). Higher PDI were observed in the polymerization of styrene. Using 1-phenyl ethylbromide (PEBr) and ethyl 2-bromoisobutyrate (EBiB) as model compounds for the polymeric chain ends, the activation rate constants of the new catalytic systems were measured. These results were correlated with the polymerization results and compared with another catalytic system previously reported.

Analysis of Tridentate Schiff Base Ni(II) Complex (세자리 Schiff Base의 Ni(II) 착물의 분석)

  • Chae, Hee-Nam;Choi, Yong-Kook
    • Analytical Science and Technology
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    • v.11 no.5
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    • pp.332-340
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    • 1998
  • Tridentate Schiff base ligands, $SIPH_2$, $SIPCH_2$, $HNIPH_2$, and $HNIPCH_2$ were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. Ni(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Ni(II) complexes were contemplated to be hexa-coordinated octahedral configuration containing three water molecules. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Ni(II) complexes were quasi-reversible and diffusion-controlled as one electron by one step process Ni(II)/Ni(I). The reduction potentials of the Ni(II) complexes shifted in the positive direction in the order [$Ni(II)(HNIP)(H_2O)_3$]>[$Ni(II)(SIP)(H_2O)_3$]>[$Ni(II)(SIPC)(H_2O)_3$]>[$Ni(II)(HNIPC)(H_2O)_3$] and their dependence on ligands were not so high. Consequently the [$Ni(II)(HNIPC)(H_2O)_3$] complex among the synthesized Ni(II) complexes was found to be most stable in the DMSO solution.

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Synthesis and Characterization of Molybdenum(V) Complexes with Tridentate Schiff Bases

  • Jung Sook Kim;Bon Kweon Koo
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.507-511
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    • 1992
  • Six-coordinate molybdenum(V) complexes X[MoO$(NCS)_2$(L)], where X=$PyH^+$, $Me_4N^+$, $Et_4N^+$, n-$Bu_4N^+$, and L= the tridentate schiff base dianions derived from the condensation reaction between various salicylaldehydes and 2-aminophenol have been synthesized. The complexes have been characterized by elemental analysis, conductivity, UV-visible, IR, $^1H$-NMR, and mass spectroscopy. The coordination around the molybdenum appears to be distorted octahedral. A tridentate ligand containing the ONO donor atoms occupies meridional positions with the N atom trans to the terminal oxo group. Two NCS ligands bond to the molybdenum through the N atom and are cis to the Mo = $O_t$ group. The electrochemical behaviors of the complexes have also been investigated by cyclic voltammetry in dimethylsulfoxide.

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.

Synthesis of Tridentate-Schiff Base Co(II) Complexes and Their Electrochemical Properties (세자리 Schiff Base Co(Ⅱ) 착물의 합성과 전기화학적 성질)

  • Chae, Hui Nam;Choe, Yong Guk
    • Journal of the Korean Chemical Society
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    • v.42 no.4
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    • pp.422-431
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    • 1998
  • Tridentate Schiff base ligands such as $SIPH_2,\;SIPCH_2,\;HNIPH_2,\;and\; HNIPCH_2$ were prepared by the reaction of salicylaldehyde and 2-hydroxy-l-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. The structures and properties of ligands and their Co(II) complexes were investigated by elemental analysis, $^1H$NMR, IR, UV-visible spectra, and thermogravimetric analysis. The molar ratio of Schiff base to the metal of complexes was found to be 1:1. Co(II) complexes were contemplated to be hexa-coordinated octahedral configuration containing three water molecules. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a supporting electrolyte were investigated by cyclic voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Co(II) complexes were irreversible and one electron processes by two steps in diffusion controlled reaction. The reduction potential of the Co(II) complexes was shifted to the positive direction in the order [Co(Ⅱ)$(HNIPC)(H_2O)_3$]>[Co(Ⅱ)$(HNIP)(H_2O)_3$]>[Co(II)$(SIPC)(H_2O)_3$]>[Co(Ⅱ)$(SIP)(H_2O)_3], and their dependence on ligands were not so high.

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The Study of Nitrogen Doner Atoms Chelating Compounds for Removing Heavy Metals (Cd2+,Pb2+,Zn2+,Cu2+) (중금속이몬(Cd2+,Pb2+,Zn2+,Cu2+)제거를 위한 질소를 주개원자로 하는 리간드들의 착화합물 형성에 관한 연구)

  • 김선덕;김준광;김정성
    • Journal of Environmental Science International
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    • v.12 no.4
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    • pp.497-501
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    • 2003
  • The new tridentate ligands of nitrogen donor atoms N,N-Bis(2-amino-ethyI)-benzyl-amine 2HCI(BABEA. 2HCI) and 2,6-Bis(amino-methyl)-pyridien. 2HCI(BAMP. 2HCI) were synthesized as their dihydrochloride salts and characterized by TA, IR. Mass and NMR spectroscopy. The protonation constants of the ligands and stability constants for Cd$^{2+}$, Pb$^{2+}$, Zn$^{2+}$and Cu$^{2+}$ ions were determined by potentiometric titration in aqueous solutions and compared with those of analogous ligands. The effect stability constants of ligands and metal ions for removal of heavy metals in aqueous solution were described.

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.