• Title/Summary/Keyword: Cobalt (II) complexes

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Kinetic Studies on the Aquation of Tetrahedral Copper (II) and Cobalt (II) Complexes (정사면체 구조를 갖는 Cu (II) 및 Co (II) 착화물들의 아쿠오화반응에 관한 연구)

  • Kim, Young-Inn;Choi, Sung-Nak;Kim, Jung-Sook;Kim, Hae-Kyung
    • Journal of the Korean Chemical Society
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    • v.32 no.2
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    • pp.122-129
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    • 1988
  • The rates of aquation of sparteine cobalt(II) halide and sparteine copper(II) halide were investigated in the citrate buffer solutions. The aquation of cobalt(II) complexes proceeds via D-mechanism and the catalytic effect of halide ions is not observed. The aquation of copper(II) complexes proceeds via $I_d$-mechanism and is catalyzed by the presence of cyanide and halide ions, and the aquation rate is pH dependent. The different mechanistic behavior of cobalt(II) complexes from corresponding copper(II) complexes seems to be attributed to the weakness of Co-N bond in the coordination sphere.

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Electrochemical Properties of Pentadentate Binucleated Schiff Base Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes in Nonaqueous Solvent (비수용매에서 이핵성 다섯자리 Schiff Base Cobalt(Ⅱ) 및 Manganese(Ⅱ) 착물들의 전기화학적 성질)

  • Ki-Hyung Chjo;Yong-Kook Choi;Song-Ju Lee;Seong-Seop Seo
    • Journal of the Korean Chemical Society
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    • v.36 no.3
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    • pp.428-441
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    • 1992
  • We synthesized a series of binuclear pentadentate Schiff base complexes such as $Co(Ⅱ)_2$ (BSPP)($H_2O)_2$, $Co(Ⅱ)_2$ (BSPD)($H_2O)_2$, $Mn(Ⅱ)_2$ (BSPP)($H_2O)_2$ and $Mn(Ⅱ)_2$ (BSPD)($H_2O)_2$, mononuclear pentadentate Schiff base complexes such as Co(Ⅱ)(BSP)($H_2O)$ and Mn(Ⅱ)(BSP)($H_2O)$. The composition of these complexes identified by IR, UV-visible spectrum, T.G.A., DSC, and elemental analysis. The electrochemical redox processes have been examined by cyclic voltammetry and differential pulse polarography with glassy carbon electrode in 0.1M TEAP-Py(-DMSO and -DMF) as a supporting electrolyte solution. As a result of electrochemical measurements, the reduction processes for pentadentate binuclear Schiff base cobalt(Ⅱ) and manganese(Ⅱ) complexes occurred to four steps in $M(Ⅲ)_2$ / $Mn(Ⅱ)_2$ and $Mn(Ⅱ)_2$ / $M(Ⅰ)_2$ (M; Co, Mn) two processes through each two reduction steps with one electron, by contrast, the mononuclear pentadentate Schiff base cobalt(Ⅱ) and manganese(Ⅱ) complexes occurred to two steps in M(Ⅲ) / M(Ⅱ) and M(Ⅱ) / M(Ⅰ) (M; Co, Mn) two processes with one electron reduction steps.

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1D and 2D Cobalt(II) Coordination Polymers, Co(ox)(en): Synthesis, Structures and Magnetic Properties

  • Kang, Jaeun;Lee, Yumi;Kim, Seungjoo;Yun, Hoseop;Do, Junghwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3244-3248
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    • 2014
  • Two ethylenediamine cobalt(II) oxalate complexes Co(ox)(en), 1 and $Co(ox)(en){\cdot}2H_2O$, 2 have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In 1, Co atoms are coordinated by two bis-bidentate oxalate ions in transconfiguration to form Co(ox) chains, which are further bridged by ethylenediamine molecules to produce 2D grid layers, Co(ox)(en). In 2, Co atoms are coordinated by bridging oxalate ions in cis-configuration to form Co(ox) chains, and the additional chelation of ethylenediamine to Co atoms completes 1D zigzag chain, Co(en)(ox). Two lattice water molecules stabilize the chains through hydrogen bonding. Magnetic susceptibility measurements indicate that both complexes exhibit weak antiferromagnetic coupling between cobalt(II) ions with the susceptibility maxima at 23 K for 1 and 20 K for 2, respectively. In 1 and 2, the oxalate ligands afford a much shorter and more effective pathway for the magnetic interaction between cobalt ions compared to the ethylenediamine ligands, so the magnetic behaviors of both complexes could be well described with 1D infinite magnetic chain model.

Metal Complexes of Ambidentate Ligands (II). Cobalt (III) and Palladium (II) Complexes of Isonitrosobenzoylacetone (Ambidentate Ligand의 금속착물 (제2보). Isonitrosobenzoylacetone 의 코발트 (III) 및 팔라듐 (II) 착물)

  • Man Ho Lee;Dae Sup Oh;Soo Han Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.121-128
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    • 1980
  • Isonitrosobenzoylacetone is particularly interesting, as the isonitroso group has two potentially coordinating sites which can compete with the cabonyl groups in forming bonds with the metal ions. In this paper tris(isonitrosobenzoylacetonato)cobalt(III) and bis(isonitrosobenzoylacetonato)palladium(II) have been prepared, and their structures have been investigated. Spectroscopic studies lead to the conclusion that the both complexes do not contain an OH group in the chelated five-membered ring structure in which the ligand coordinates to metal through oxygen of the acetyl group and nitrogen of the isonitroso group. The coordination manner of this ligand is similar to that of isonitrosobenzoylacetone obtained by Patel and Haldar.

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Electrochemical Properties of Binuclear Cobalt (II) Complexes with Tetradentate Schiff Base in Aprotic Solvents (III) (비수용매에서 이핵성 네자리 Schiff Base Cobalt(II) 착물들의 전기화학적 성질 (제 3 보))

  • Chjo Ki-Hyung;Choi Yong-Kook;Seo Seong-Seob;Lee Song-Ju
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.379-388
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    • 1991
  • We synthesized the binuclear Tetradentate Schiff base cobalt (II) complexes; [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] (where, SMPD: N,N'-bis(salicylaldehyde)-m-phenylenediimine, SPPD: N,N'-bis(salicylaldehyde)-p-phenylenediimine, L: Py, DMSO and DMF). We identified the binuclear structure of these complexes by elemental analysis, IR-spectrum, and T. G. A. According to the results of cyclic voltammetry and DPP measurements in aprotic solvents containing 0.1M TEAP as supporting electrolyte, it was found that diffusionally controlled redox process of two step for one electron was reversible or quasi reversible process in 0.1M TEAP-pyridine and 0.1M TEAP-DMSO solution at mononuclear complexes; [Co(II)(SOPD)(L)$_2$]. But, we knew that diffusionally controlled reduction processes of four steps with one electron for binuclear [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] complexes was Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$ in aprotic solvents.

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Isotropic NMR Shifts in Some Pyridine-Type Ligands Complexed with Paramagnetic Undecatungstocobalto(Ⅱ)silicate and Undecatungstonickelo(Ⅱ) silicate Anions. Identifications of Dumbbell-Shaped 4,$4^{\prime}$-Bipyridyl Complexes

  • Moonhee Ko;Gyung Ihm Rhyu;Hyunsoo So
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.500-506
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    • 1993
  • $^1H$ and $^{13}C$ NMR spectra for pyridine, ${\beta}$-and ${\gamma}$-picoline, pyrazine, and 4,4'-bipyridyl complexed with paramagnetic undecatungstocobalto(II)silicate and undecatungstonickelo(II)silicate anions are reported. For these complexes the ligand exchange is slow on the NMR time scale and the pure resonance lines have been observed at room temperature. The isotropic shifts in nickel complexes can be interpreted in terms of contact shifts by ${\sigma}$-electron delocalization. Both contact and pseudocontact shifts contribute to the isotropic shifts in cobalt complexes. The contact shifts, which are obtained by subtracting the pseudocontact shifts from the isotropic shifts, require both ${\sigma}$-and ${\pi}$-electron delocalization from the cobalt ion. Slow ligand exchange has also allowed us to identify the species formed when bidentate ligands react with the heteropolyanions. Pyrazine forms a 1 : 1 complex, while 4,4'-bipyridyl forms both 1 : 1 and dumbbell-shaped 1 : 2 complexes.

Electrochemical Reduction for trans-Complexes of Cobalt (III) with Bis(ethylenediamine) and Monodendate Ligands (한자리 리간드를 포함하는 트란스비스 (에틸렌디아민) 코발트 (III) 이온의 전극 환원반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Jae-Duck Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.215-224
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    • 1989
  • Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

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Studies on Interaction of Essential Metal Ions with Bioactive Ligands

  • Tewari, Brij Bhushan
    • Bulletin of the Korean Chemical Society
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    • v.25 no.6
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    • pp.809-812
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    • 2004
  • Complexation reactions of nitrilotriacetate (NTA) and penicillamine with $Cu^{2+}$ and $Co^{2+}$ have been studied in solution phase using paper electrophoresis technique. The stability constants of the complexes Cu(II)-nitrilotriacetate-penicillamine and Co(II)-nitrilotriacetate-penicillamine have been found to be $6.64{\pm}0.03\;and\;5.86{\pm}0.05$ (logarithm stability constant values), respectively at 35$^{\circ}C$ and ionic strength 0.1 M.

The Kinetics of Complexation of Nickel(II) and Cobalt(II) Mandelates in Aqueous Solution

  • Choi, Ki-Young;Yun, Sock-Sung;Kim, Mal-Jin
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.629-632
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    • 1991
  • The rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with mandelate have been determined by the pressure-jump relaxation study. The forward and reverse rate constants for the mandelate complex formation reactions were obtained to be $k_f=3.60{\times}10^4\;M^{-1}s^{-1}$ and $k_r=1.73{\times}10^2\;s^{-1}$ for the nickel(II), and $k_f=1.75{\times}10^5\;M^{-1}s{-1}$ and $2.33{\times}10^3\;s^{-1}$ for the cobalt(II) in aqueous solution of zero ionic strength ($(\mu{\to}0)\;at\;25^{\circ}C$. The results were interpreted by the use of the multistep complex formation mechanism. The rate constants evaluated for each individual steps in the multistep mechanism draw a conclusion that the rate of the reaction would be controlled by the chelate ring closure step in concert with the solvent exchange step in the nickel(II) complexation, while solely by the chelate ring closure step for the cobalt(II) complex.