• Title/Summary/Keyword: Co(II) complex

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Transition Metal Catalysed Oxidation Reactions and Ligand Effects in Aprotic Solvents (전이금속 촉매작용의 산화반응과 리간드 효과)

  • Kim, Sang-Bock
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.585-590
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    • 2003
  • Cobalt oxygen carrier complex N,N'-ethylenebis(3-methoxysalycylideneiminato)cobalt(II), Co(3MeOsalen) was prepared at $25{\circ}C$. UV and visible absorption spectra of the complex and hydrazobenzene were studied in non-aqueous solvent methanol in the range of wavelength 200-600 nm. The oxidation of hydrazobenzene by oxygen in non-aqueous solvent is catalysed by Co(3MeOsalen). In the presence of triphenylphosphine($PPh_3$), the rate decreases in methanol. This is presumably attributable to the coordination of $PPh_3$ to the Co(3MeOsalen), resulting in the catallytically inactive compound. The initial rates of the oxidation of hydrazobenzene with the ligand triphenylphosphine were measured by the theoretical values of the rates, Rate=$k_1+k_2K_1[P]/1+K_1[P]+K_1K_2[P]^2$. This fact would be a poorer σ-donor ligand than methanol.

Synthesis, Characterization and Biological Activities of 4-(p-Chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide and Its Metal Complexes

  • Hassanien, Mohammad M.;Mortada, Wael I.;Hassan, Ali M.;El-Asmy, Ahmed A.
    • Journal of the Korean Chemical Society
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    • v.56 no.6
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    • pp.679-691
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    • 2012
  • New series of metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Pd(II) and Pt(II) with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) have been synthesized and characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, $^1H$ NMR, mass and ESR) and thermal studies. The IR data suggest different coordination modes for HCPTS which behaves as a monobasic bidentate with all metal ions except Cu(II) and Zn(II) which acts as a monobasic tridentate. Based on the electronic and magnetic studies, Co(II), Cu(II), Pd(II) and Pt(II) complexes have square - planner, Ni(II) has mixed stereochemistry (tetrahedral + square planar), while Zn(II) is tetrahedral. Molar conductance in DMF solution indicates the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complex show $g_{\parallel}$ (2.2221) > $g_{\perp}$ (2.0899) > 2.0023 indicating square-planar structure and the presence of the unpaired electron in the $d_x2_{-y}2$ orbital with significant covalent bond character. The thermal stability and degradation kinetics of the ligand and its metal complexes were studied by TGA and DTA and the kinetic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The complexes have more antibacterial activity against some bacteria than the free ligand. However, the ligand has high anticancer activities against HCT116 (human colon carcinoma cell line) and HEPG2 (human liver hepatocellular carcinoma cell line) compared with its complexes.

Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.919-925
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    • 2011
  • A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UV-VIS, $^1H$- and $^{13}C$- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in $CD_3OD+10%D_2O$ after exposure to $^{60}Co-{\gamma}$-rays at 77 K using a 0.2217 M rad $h^{-1}$ vicrad source showed $g_{\perp}$ > $g_{\parallel}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_z2$ orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with ${\gamma}$-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the $dz^2$ orbital occurs. However, the ESR spectrum in solid state after exposure to $^{60}Co-{\gamma}$-rays at 77 K showed $g_{\parallel}$ > $g_{\perp}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_x2_{-y}2$ ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, $[H_{12}LMn]Cl_4.2H_2O$, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, $[H_{12}LFe]Cl_5.H_2O$, showed spectrum of a high spin $^{57}Fe$ (I=1/2), $d^5$ configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

Synthesis and Structure of Nickel(II) Complex with N-Benzylisonitrosoacetylacetone Imine (N-Benzylisonitrosoacetylacetone Imine Ni(II) 착물의 합성 및 구조)

  • Byung Kyo Lee;Dae Sub O;Heung Lark Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.6
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    • pp.536-542
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    • 1988
  • A nickel(Ⅱ) complex, Ni(IAA-NBz) (IAA-NBz') with ligand, N-benzylisonitrosoacetyl acetone imine (H-IAA-NBz) has been synthesized. This complex is very stable at room temperature and has cis-form and trans-form isomers. The ratio of nickel (Ⅱ) ion and ligand combined is 1 : 2. The elemental analysis, ir, nmr. electronic spectra and mass spectra have been studied. It is suggested from these studies that the isonitroso group of one ligand, H-IAA-NBz coordinates to nickel(Ⅱ)ion through the nitrogen atom to form five-membered ring, while that of the other ligand, H-IAA-NBz coordinates to nickel (Ⅱ) ion through the oxygen atom to form six-membered ring in square-planar complex.

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A Study on the Adsorption of Hg(II) Ion by Activated Carbon(1) (活性炭에 依한 Hg(II) 이온의 吸着에 관한 조사연구(1))

  • Lee, Hyun;Lee, Jong-Hang;Yun, O. Sub
    • Journal of Environmental Health Sciences
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    • v.14 no.2
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    • pp.65-71
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    • 1988
  • In this study, the method of adsorption by activated carbon in the removal of Hg(II) ion in waste water was treated. The influence of kinds of activated carbon and effect of temperature and the influence of coexistent salt on adsorption rates, the influence of pH in the adsorption, equilibrium and adsorption of mercury from activated carbon were investigated. From the adsorption on activated carbon of mercury(II) ion in the presence of cyanide or thiocyanate ion was found that mercury(II) was easily adsorved onto the activated carbon in the form of complex artion such as Hg(CN)$_4^{2-}$, Hg(SCN)$_4^{2-}$ respectively. ZnCl$_2$ activation method had a higher adsorptive ability than steam activation method in adsorption of Hg on activated carbon. Activated carbon adsorbed iodide ion is very effective on adsorption of Hg.

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Complexation of Cadmium(Ⅱ) with Humic Acids: Effects of pH and Humic Acid Origin

  • Lee, Mee-Hae;Choi, Se-Young;Chung, Kun-Ho;Moon, Hi-Chung
    • Bulletin of the Korean Chemical Society
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    • v.14 no.6
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    • pp.726-732
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    • 1993
  • A comparative study on cadmium(II) complexation with three well characterized humic acids (SHA: soil humic acid from the Okchun Metamorphic Belt; AqHA: aquatic humic acid from Gorleben underground aquifer, Germany; CoHA: commercially available humic acid from the Aldrich Co.) was carried out in 0.1 M $NaClO_4$ at different solution pH(5.0, 5.5, and 6.0) using the ultrafiltration technique. The maximum binding ability (MBA) of the humic acids for cadmium(II) was observed to vary with their origins and solution pH. The results suggest that 1 : 1 complex predominates within the experimental range, and the conditional stability constants were calculated based on the assumption of cooperative binding, yielding log K values that were quite similar (CoHA: 4.17${\pm}$0.08; AqHA: 4.14${\pm}$0.07; SHA: $4.06{\pm} 0.12\;l\;mol^{-1}$ at pH 6.0) irrespective of humic acid origins or pH. By contrast a nonlinear Schatchard plot was obtained, using the cadmium(II) ion selective electrode speciation analysis method, which indicated that humic acid may have two or more classes of binding sites, with $log\;K_1\;and\;log\;K_2$ of 4.73${\pm}$ 0.08 and $3.31{\pm}0.14\;l\;mol^{-1}$ respectively.

Formation of Cadmium(II) Nitrate Complexes with Macrocycles

  • Ho-Doo Kim;Hak-Jin Jung;Oh-Jin Jung
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.561-567
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    • 1993
  • The twelve macrocycle (L) complexes of cadmium(II) nitrate have been synthesized: $CdL(NO_3)_2$. All the complexes have been indentified by elemental analysis, electric conductivity measurements, IR and NMR spectroscopic techniques. The molar electric conductivities of the complexes in water and acetonitrile solvent were in the range of 236.8-296.1 $cm^2{\cdot}mol^{-1}{\cdot}ohm^{-1}$ at 25$^{\circ}$C. The characteristic peaks of macrocycles affected from Cd(II) were shifted to lower frequencies as compared with uncomplexed macrocycles. A complex with 1,4,8,11-tetrakis(methylacetato)-1,4,8,11-tetraaza cyclodecane (L4) exhibited two characteristic bands such as strong stretching (1646 $cm^{-1})$, and weaker symmetric stretching band (1384 $cm^{-1})$. NMR studies indicated that all nitrogen donor atoms of macrocycles have greater affinity to cadmium(II) metal ion than do the oxygen atoms. The $^{13}$C-resonance lines of methylene groups neighboring the donor atom such as N and S were shifted to a direction of high magnetic field and the order of chemical shifts were $L_1 < L_2 < L_3 < L_6 < L_4$. Also the chemical shifts values were larger than those of methylene groups bridgeheaded in side-armed groups. This result seems due to not only the strong interaction of Cd(Ⅱ) with nitrogen donors according to the HSAB theory, but weak interaction of Cd(Ⅱ) and COO- ions or sulfur which is enhanced by the flexible methylene spacing group in side-armed groups. Thus, each additional gem-methyl pairs of L_3, L_4\;and\; L_6$ macrocycles relative to $L_1, L_2,\;and\;L_5$ leads to an large enhancement in Cd(II) affinity. ^{13}C$-NMR spectrum of the complex with $L_{12}$ (1,5,9,13-tetracyclothiacyclohexadecane-3,11-diol) reveals the presence of two sets of three resonance lines, and intensities of the each resonance line have the ratio of 1 : 2 : 2. This molecular conformation is predicted as structure of tetragonal complex to be formed by coordinating two sulfur atoms and the other two sulfur atoms which is affected by OH-groups.

Spectrophotometric Determination of Palladium after Solid-liquid Extraction with 4-(2-Pyridylazo)-resorcinol at 90°C

  • Dong, Yanjie;Gai, Ke
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.943-946
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    • 2005
  • An effective spectrophotometric determination of palladium with 4-(2-pyridylazo)-resorcinol (PAR) using molten naphthalene as a diluent has been studied. A red complex of palladium with PAR is formed at 90 ${^{\circ}C}$. In the range of pH 9.0-11.0, the complex is quantitatively extracted into molten naphthalene. The organic phase is anhydrously dissolved in $CHCl_3$ to be determined spectrophotometrically at 520 nm against the reagent blank. Beer’s law is obeyed over the concentration range of 0.1-2 ${\mu}g{\cdot}mL^{-1}$. The molar absorptivity and Sandell’s sensitivity are 8.0 ${\times}\;10^5\;L{\cdot}mol^{-1}{\cdot}cm^{-}1\;and\;0.49\;{\mu}g{\cdot}cm^{-2}$ respectively. From the results of tolerance limits, it was found that there was no interferences were observed for most of the ions examined and those somewhat high interferences by Co(II), Fe(II) and Bi(III) could be effectively masked by EDTA.

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.

Synthesis of Novel Electrochemiluminescent Polyamine Dendrimers Functionalized with Polypyridyl Ru(II) Complexes and Their Electrochemical Properties

  • Lee, Do-Nam;Park, Hee-Sang;Kim, Eun-Hwa;Jun, Young-Moo;Lee, Ja-Young;Lee, Won-Yong;Kim, Byeong-Hyo
    • Bulletin of the Korean Chemical Society
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    • v.27 no.1
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    • pp.99-105
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    • 2006
  • Polyamine dendrimers functionalized with electrochemiluminescent (ECL) polypyridyl Ru(II) complexes, dend-$[CO-(CH_2)_3-mbpy{\cdot}Ru(L)_2]_3(PF_6)_6$ (dend: N$(CH_2CH_2NH)_3$-, L: bpy, o-phen, phen-Cl, DTDP), were synthesized through the complexation of dendritic polypyridyl ligands to Ru(II) complexes. Their electrochemical redox potentials, photoluminescence (PL), and relative ECL intensities were studied. The ECL emissions produced by the reaction between the electro-oxidized $Ru^{3+}$ species of polyamine dendrimers and tripropylamine as a coreactant were measured in a static system with potential cycles between 0.8 and 1.3 V or through flow injection analysis with a potential of +1.3 V, and were compared to that of $[Ru(o-phen)_3](PF_6)_2{\cdot}Dend-[CO-(CH_2)_3-mbpy{\cdot}Ru(bpy)_2]_3(PF_6)_6$ showed an ECL intensity that was two-fold greater than that of the reference complex $[Ru(o-phen)_3](PF_6)_2$.