• Title/Summary/Keyword: Transition-metal complexes

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Synthesis, Potentiometric, Spectral Characterization and Microbial Studies of Transition Metal Complexes with Tridentate Ligand (세자리 리간드의 전이금속 착물에 대한 합성과 전위차 및 분광학적 확인 그리고 미생물학적 연구)

  • Jadhav, S.M.;Munde, A.S.;Shankarwar, S.G.;Patharkar, V.R.;Shelke, V.A.;Chondhekar, T.K.
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.515-522
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    • 2010
  • A relation between antimicrobial activities and the formation constants of solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with tridentate Schiff base ligand, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2Hpyran-2-one (HL) derived from o-phenylene diamines, dehydroacetic acid (DHA) and p-chloro benzaldehyde have been studied. The ligand and metal complexes were characterized by elemental analysis, conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, $^1H$-NMR, UV-vis and mass spectra. From the analytical data, the stiochiometry of the complexes was found to be 1:2 (metal:ligand) with octahedral geometry. The molar conductance values suggest the nonelectrolytic nature of metal complexes. The X-ray diffraction data suggests monoclinic crystal system for Ni(II) and orthorhombic crystal system for Cu(II) and Co(II) complexes. The IR spectral data suggest that the ligand behaves as tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behavior (TG/DTA) and kinetic parameters calculated by Coats-Redfern method suggests more ordered activated state in complex formation. The protonation constants of the complexes were determined potentiometrically in THF:water (60:40) medium at $25^{\circ}C$ and ionic strength ${\mu}=0.1\;M$ ($NaClO_4$). Antibacterial activities in vitro were performed against Staphylococcus aureu and Escherichia coli. Antifungal activities were studied against Aspergillus Niger and Trichoderma. The effect of the metal ions and stabilities of complexes on antimicrobial activities are discussed.

Theoretical Study of C-H σ-Bond Activation and Related Reactions

  • Sakaki, Shigeyoshi
    • Bulletin of the Korean Chemical Society
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    • v.24 no.6
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    • pp.829-831
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    • 2003
  • Various theoretical studies of σ-bond activation of organic molecules by transition metal complexes arereviewed. In the homolytic σ-bond activation, the d orbital energy level of the central metal is an importantfactor, as well known. At the same time, the electron-withdrawing substituent which stabilizes the sp3 orbitalaccelerates the homolytic σ-bond activation. In the heterolytic C-H σ-bond activation of RH by $MXL_n$, the XHbond formation is an important driving force, where $MRL_n$ and HX are formed as products. The heterolytic σ-bond activation is also understood in terms of the electrophilic attack of the metal center to the substrate.

Transition Metal Complexes Derived From 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide Synthesis, Structural Characterization, and Biological Activities

  • Alhakimi, Ahmed N.;Shakdofa, Mohamad M.E.;Saeed, S. El-Sayed;Shakdofa, Adel M.E.;Al-Fakeh, Maged S.;Abdu, Ashwaq M.;Alhagri, Ibrahim A.
    • Journal of the Korean Chemical Society
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    • v.65 no.2
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    • pp.93-105
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    • 2021
  • Mononuclear Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Fe(III), Ru(III), and UO2(II) complexes of 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide (H2L) were prepared by direct method. The ligand and its complexes were isolated in solid state and characterized by analytical techniques such as elemental and thermal analyses, molar conductance, magnetic susceptibility measurements and spectroscopic techniques such as UV-Visible, IR, 1H-NMR and 13C-NMR. The spectral data indicated that the ligand acted as neutral/monobasic bidentate or monobasic/dibasic tridentate ligand bonded to the metal ions through the oxygen atom of ketonic or enolic carbonyl group, azomethine nitrogen atom and deprotonated/protonated phenolic oxygen atom forming either tetragonally distorted octahedral or octahedral. Antimicrobial activities of the ligand and its complexes were evaluated against Escherichia coli, Bacillus subtilis and Aspergillus niger by well diffusion method. The results of antifungal activity showed that the Fe(III) complex (10) exhibited higher antifungal against Aspergillus niger than the other complexes. However, the results of antibacterial activity revealed that Cu(II) complex (4) is the most active against Escherichia coli while the Cu(II) complex (5) and Fe(III) complex (10) exhibited higher antibacterial effect on Bacillus subtilis than the other complexes.

Preparation of Dioxygen Bridged Palladium Complexes by Superoxide Ion $(O_2^-)$ (초과산화이온 $(O_2^-)$ 에 의한 산소가교팔라듐착화합물의 합성)

  • Pyeong Jin Chung
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.135-142
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    • 1984
  • New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

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Cytotoxic Effects of Some Transition Metals, Nickel(II), Copper(II) and Zinc(II), with 3.6-bis(2'-pyridyl)pyridazines Complexes (몇 가지 전이금속, Ni(II), Cu(II) 및 Zn(II) 3,6-bis(2'-pyridyl)pyridazine 착 화합물들의 세포 독성효과)

  • Kwon, Byung-Mok;Lee, Chong-Ock;Choi, Sang-Un;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.49 no.1
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    • pp.21-24
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    • 2006
  • A series of cytotoxic activities $(ED_{50})$ in vitro against six human cancers (lung cancer, uterine cancer, skin cancer, brain cancer, colon cancer and adenocarcinoma) and their seventeen cell lines of 3,6-bis(2'-pyridyl)pyridazine, 1, 3,6-bis-(6'-methyl-2'-pyridyl)pyridazine, 2 and their transition metal, Ni(II), Cu(II) and Zn(II) complexes, $3{\sim}6$ were measured. Particularly, the results revealed that the cytotoxic activities against the brain cancer cell line (SNB-19) and the colon cancer cell line (SW62) of bis- [3,6-bis-(6'-methyl-2'-pyridyl)pyridazine-$k^2N^2,N^3$]chlorocopper(II)perchlorate, 4 were shown to be higher than that of the first generation anticancer agent, Cis-platin.

Synthesis and Photovoltaic Performance of Long Wavelength Absorption Dyes for the Dye Sensitized Solar Cell (장 파장 대 태양광을 흡수하는 염료감응형태양전지에 대한 염료와 합성)

  • Kim, Sangah;Yoon, Jooyoung;Kim, Jaehong
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.89.2-89.2
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    • 2010
  • The dye-sensitized solar cell (DSSC) is a device for the conversion of visible light into electricity, based on the sensitization of wide bandgap semiconductors. The performance of the cell mainly depends on a dye used as sensitizer. The absorption spectrum of the dye and the anchorage of the dye to the surface of $TiO_2$ are important parameters determining the efficiency of the cell. Generally, transition metal coordination compounds(ruthenium polypyridyl complexes) are used as the effective sensitizers, due to their intense charge-transfer absorption in the whole visible range and highly efficient metal-to ligand charge transfer. However, ruthenium polypyridyl complexes contain a heavy metal, which is undesirable from point of view of the environmental aspects. Moreover, the process to synthesize the complexes is complicated and costly. Alternatively, organic dyes can be used for the same purpose with an acceptable efficiency. The advantages of organic dyes include their availability and low cost. We designed and synthesized a series of organic sensitizers containing long wavelength absorption-chromophores for the dye sensitized solar cell. The DSSC composed of Blue-chromophores for the sensitization absorbed long wavelength region which is different also applied into the dye-cocktail (mixing) system. The photovoltaic property of DSSCs organic long wavelength absorption-chromophores were measured and evaluated by comparison with that of individual chromophores.

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Synthesis and Photovoltaic Performance of NIR Absorption Dyes for the Dye Sensitized Solar Cell (NIR 흡수 염료를 이용한 염료감응형 태양전지)

  • Kim, Sangah;Jung, Miran;Lee, Minkyung;Kim, Jaehong
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.118.1-118.1
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    • 2011
  • The dye-sensitized solar cell (DSSC) is a device for the conversion of visible light into electricity, based on the sensitization of wide bandgap semiconductors. The performance of the cell mainly depends on a dye used as sensitizer. The absorption spectrum of the dye and the anchorage of the dye to the surface of TiO2 are important parameters determining the efficiency of the cell. Generally, transition metal coordination compounds(ruthenium polypyridyl complexes) are used as the effective sensitizers, due to their intense charge-transfer absorption in the whole visible range and highly efficient metal-to ligand charge transfer. However, ruthenium polypyridyl complexes contain a heavy metal, which is undesirable from point of view of the environmental aspects. Moreover, the process to synthesize the complexes is complicated and costly. Alternatively, organic dyes can be used for the same purpose with an acceptable efficiency. The advantages of organic dyes include their availability and low cost. We designed and synthesized a series of organic sensitizers containing long wavelength absorption-chromophores for the dye sensitized solar cell. The DSSC composed of Blue-chromophores for the sensitization absorbed long wavelength region which is different also applied into the dye-cocktail (mixing) system. The photovoltaic property of DSSCs organic long wavelength absorption-chromophores were measured and evaluated by comparison with that of individual chromophores.

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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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Allyloxy-and Benzyloxy-Substituted Pyridine-bis-imine Iron(II) and Cobalt(II) Complexes for Ethylene Polymerization

  • Kim Il;Han Byeong Heui;Kim Jae Sung;Ha Chang-Sik
    • Macromolecular Research
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    • v.13 no.1
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    • pp.2-7
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    • 2005
  • A series of ethylene polymerization catalysts based on tridentate bis-imine ligands coordinated to iron and cobalt was reported. The ligands were prepared through the condensation of sterically bulky anilines with allyloxy-and benzyloxy-substituted 2,6-acetylpyridines. The pre-catalyst complexes were penta-coordinate species of the general formula $\{[(ArN=C(Me))_2(4-RO-C_5H_3N)]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; R=allyl, benzyl; M=Fe, Co). In the presence of ethylene and methyl alumoxane cocatalysts, these complexes were active for the polymerization of ethylene, with activities lower than those of metal complexes of the general formula $\{[(2-ArN=C(Me)_2C_5H_3N]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; M=Co, Fe), containing no substituents in 2,6-acetylpyridine ring. The effects of the catalyst structure and temperature on the polymerization activity, thermal properties, and molecular weight were discussed.