• Title/Summary/Keyword: Tridentate

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Theoretical Studies on MXO4 (M=Li, Na, K and X=F, Cl, Br, I) Salt Ion Pairs

  • Rashid, Mohammad Harun Or;Ghosh, Manik Kumer;Choi, Cheol-Ho
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2215-2218
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    • 2010
  • The series of alkali metal perhalogenates, $MXO_4$ (M=Li, Na, K and X=F, Cl, Br, I) were theoretically studied with the help of MP2 methods. Bidentate as well as tridentate structures were found to be stable minima. The bidentate structures are becoming preferred as the size of halogen increases and as the size of metal decreases. Geometrically, the M-O and M-X distances of both bidentate and tridentate structures, increase with the size of metal. Generally, the M-$O_1$ distances of tridentate forms are longer than the corresponding distances of bidentate forms, while the M-X distances of tridentate forms show the opposite trend. Similarly, the X-O bonds increase with the size of halogens except $MXO_4$ pairs, where the X-O bonds are unusually long due to the enhanced oxygen-oxygen repulsions. In short, the relative energetics as well as the geometrical parameters are found to be strongly dependent on halogen and metal elements.

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.

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.

$^{13}C$ and $^{51}V$ Nuclear Magnetic Resonance Studies of Vanadium(V) Complexes of Iminodiacetate Analogues

  • Lee, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.22-26
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    • 1992
  • The solution structures of the vanadium(V) complexes of iminodiacetate analogues, such as iminodiacetate (IDA), methyliminodiacetate (MeIDA), ethyliminodiacetate (EtIDA), benzyliminodiacetate (BzIDA), pyridine-2,6-dicarboxylate (DPA), and 2-hydroxyethyliminodiacetate (HEIDA), have been studied by $^{13}C-$ and $^{51}V$-NMR spectroscopy. Assuming that the complexes have a $cis-VO_2$ core, IDA, MeIDA, EtIDA, and BzIDA act as facial tridentate ligands to form octahedral complexes, whereas DPA coordinates to $VO_2^+$ as a meridional tridentate. And one water molecule fulfills the remaining site to satisfy the coordination number of six. But HEIDA coordinates to $VO_2^+$ through one IDA moiety and one hydroxyl group, acting as a tetradenate.

First Example of Monometallic Palladium(II) Compound with Trans-Chelating Tridentate Ligand: Synthesis, Crystal Structure, and Characterizations

  • Tae Hwan Noh
    • Mass Spectrometry Letters
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    • v.14 no.3
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    • pp.110-115
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    • 2023
  • The reaction of (COD)PdCl2 with new C3-symmetric tridentate L (COD = 1,5-cyclooctadien; L = 1,3,5-tris(picolinoyloxyethyl)cyanurate) in a mixture of acetone and dichloromethane produces single crystals consisting of unprecedented monometallacyclic [PdCl2(L)]. This cyclic compound arises from trans-chelation of two of three donating pyridyl groups of L, while the third pyridyl group remains uncoordinated. Electrospray ionization mass spectrometry (ESI-MS) data on L exhibited the major peak corresponding to [C27H24N6O9 + H+]+. Fast atom bombardment mass spectrometry (FABMS) data on [PdCl2(L)], however, showed the mass peak corresponding to the L instead of the present palladium(II) compound species, due to the insolubility and dissociation in solution. The physicochemical properties of the present palladium(II) compound were fully characterized by means of infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, thermal analysis, single-crystal X-ray diffraction (SC-XRD) measurement.

Studies on the Cu (II), Ni (II) and Zn (II) Complexes with Tridentate Schiff Base Ligand (I) (세자리 Schiff Base 리간드의 Cu (II), Ni (II) 및 Zn (II) 착물에 관한 연구 (제1보))

  • Chjo Ki Hyung
    • Journal of the Korean Chemical Society
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    • v.18 no.3
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    • pp.189-193
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    • 1974
  • The tridentate schiff base, salicylidene imino-o-thiolbenzene, has been synthetized from salicylaldehyde and o-amino thiolbenzene by Duff reaction. The schiff base has been reacted with Cu(II), Ni(II), and Zn(II), to form new complexes; Cu(II)$[C_{13}H_9ONS]{\cdot}3H_2O$, Ni(II)$[C_{13}H_9ONS]{\cdot}3H_2O,\;Zn(II)[C_{13}H_9ONS]{\cdot}3H_2O$ It appears that the Cu(II)-complex has tetra-coordinated configuration with the schiff base and one molecule of water, while the Ni(II) and Zn(II)-complexes have hexacoordinated configuration with the schiff base and three molecules of water. The mole ratio of tridentate schiff base ligand to metals was 1:1. These complexes have been identified by infrared spectra, visible spectra, TGA, DTA and elemental analysis.

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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).

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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