• Title/Summary/Keyword: Co(III) Complex

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Studies on Electroanalytical Chemistry for the Oxygen Adducted Tetradentate Schiff base Cobalt(III) Complexes in Pyridine Solution (Pyridine 용액에서 산소 첨가된 네자리 Schiff base Cobalt(III) 착물들의 전기 분석화학적 연구)

  • Rim, Chae-Pyeong;Chae, Hee-Nam;Chjo, Ki-Hyung;Choi, Yong-Kook
    • Analytical Science and Technology
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    • v.8 no.1
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    • pp.55-62
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    • 1995
  • Tetradentate Schiff base cobalt(II) complexes such as $Co(II)_2-N$, N-bis(salicylidene)-m-phenylendiimine; [$Co(II)_2(SMPD)_2(H_2O)_4$] and $Co(II)_2-N$, N-bis(salicylidene)-p-phenylendiimine: [$Co(II)_2(SPPD)_2(H_2O)_4$], and oxygen adducted cobalt (III) complexes such as [$Co(III)_2O_2(SMPD)_2(Py)_2$] and [$Co(III)_2O_2(SPPD)_2(Py)_2$] in pyridine solutions were synthesized. It was identified that the oxygen adducted cobalt(III) complexes have hexacoordinated octahedral configuration with pyridine and oxygen from the measurement of elemental analysis, AA, IR spectra, and TGA. The redox processes were investigated for the oxygen adducted complexes in 0.1M TEAP-pyridine solution, using cyclic voltammetry on the glassy carbon electrode. The redox processes of oxygen adducted Co(III) complexes result in $$[Co(III)_2-O_2-CO(III)]\rightarrow^{e^-}[Co(III)-O_2-Co(II)]\rightarrow^{e^-}[Co(II)-O_2-Co(II)]\rightleftarrows^{e^-}[Co(II)+Co(II)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(II)+Co(I)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(I)+Co(I)+O_2{\cdot}^-]$$.

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Studies on The Electrochemical Properties of Oxygen adducts Tetradentate Schiff Base Cobalt(II) Complexes in DMSO (I) (DMSO용액에서 네자리 Schiff Base Cobalt(II) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 1 보))

  • Chjo Ki-Hyung;Jin-Soon Chung;Heui-Suk Ham;Seoing-Seob Seo
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.542-554
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    • 1987
  • Tetradentate schiff base cobalt(II) complexes; Co(SED), Co(SND) and Co(SOPD) have been prepared, these complexes have react with dry oxygen in DMSO to form oxygen adducts cobalt(III) complexes; $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ and $[Co(SOPD)(DMSO)]_2O_2$. It seems to be that the oxygen adducts cobalt(Ⅲ) complexes have heexa coordinated octahedral configration with tetradentate schiff base cobalt (III), DMSO and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1 : 2, these complexes have been identified by IR-Spectra, T.G.A., magnetic susceptibilitis and elemental analysis of C.H.N. and Cobalt. The redox reaction process of Co(SED), Co(SND) and Co(SOPD) complexes was investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP-DMSO. The results of redox reaction process of Co(II) / Co(III) and Co(II) / Co(I) for cobalt(SED) and cobalt(SOPD) complexes and Co(II) / Co(III) process for cobalt(SND) complex are reversible process but Co(II) / Co(I) process of Cobalt(SND) complex is irreversible, and oxygen adduct complexes to quasi reversibly with oxygen should be very closed related to the redox potentials of range, $E_{pc}$ = -0.80~-0.89V and $E_{pa}$ = -0.70~-0.76V.

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Molecular Oxygen in Solid State of Polymeric Tetraphenylporphinatocobalt(II) (고분자로 지지된 코발트(II) 테트라페닐포피린 화합물에서의 산소분자에 관한 연구)

  • Chae Hee Kwon;Chong Soo Han;Hakze Chon
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.114-120
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    • 1984
  • The reversible oxygenation of a solid stae polymeric cobalt(II) porphyrin complex, PVP-CoTPP was studied at 0, -24 and $-78^{\circ}C$. When PVP-CoTPP was contacted with $O_2 $at$-78^{\circ}C$ the oxygen uptake increased with oxygen partial pressure. At about 700mmHg $O_2$, the amount of oxygen taken up corresponded approximately one oxygen molecule to one Co(II) complex. The amount of $O_2$ taken up by PVP-CoTPP decreased with increasing temperature. When $16O_2$ was admitted to the Co(II) complex a EPR signal corresponding to $O_2^-$ increased with a decrease in Co(II) signal. The results suggest that an electron is transfered from Co(II) in PVP-CoTPP to oxygen forming a $Co(III)-O_2^-$ complex where $O_2^- $is superoxide type.

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N,N'-Dimethylethylenediamine-N,N'-di-α-butyric Acid Cobalt(III) Complexes Utilizing Oxidation of Sulfur of S-Methyl-L-cysteine

  • Kim, Hyun-Jin;Youm, Kyoung-Tae;Yang, Jung-Sung;Jun, Moo-Jin
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.851-856
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    • 2002
  • The Reaction of S-methyl-S-cysteine(L-Smc) with racemic $s-cis-[Co(demba)Cl_2]-1$ (Hydmedba = $NN'-dimethylethylenediamine-NN'-di-\alpha-butyric$, acid) yields ${\Delta}$-s-cis-[Co(dmedba)(L-Smc)] 2 with N, O-chelation. Oxidation of sulfur of 2 with $H_2O_2$ in a 1 : 1 mole ratio gives ${\Delta}$-s-cis[Co(dmedba)(L-S(O)mc)] 3 having an uncoordinated sulfenate group. Oxidation of sulfur of L-Sm with $H_2O_2in$ a 1: 1 mole ratio produces S-methyl-L-cysteinesulfenate (L-S(O)me) 5. Direct reaction of 1 with 5 in basic medium gives an N.O-chelated ${\Delta}$s-cis[Co(dmedba)(L-S(O)mc)-N.O], which turmed out be same as obtained by oxidation of 2, while an N, S-chelated ${\Delta}$-s-cis-[Co(dmedba)(S-S(O)mc)-N,O] complex 4 is obtained in acidic medium from the reaction of 1 with 5. This is one of the rare $[$Co^{III}$(N_2O_2-type$ ligand)(amino acid)] type complex preparations, where the reaction conditions determine which mode of N, O and N, S caelation modes is favored.

Cobalt(III) Complexes Containing Ethylenediamine-Triacetate and Aliphatic Diamine (I). The Reaction of Etylenediamine-tetraacetatocobaltate(Ⅲ) with Trimethylenediamine in Aqueous Solution (지방족디아민과 에틸렌디아민-트리아세테이트를 포함하는 코발트 (Ⅲ) 錯物에 관한 연구 (제1보). 수용액 중에서 [Co(EDTA)]- 錯物에 트리메틸렌디아민의 반응)

  • Myung-Ki Doh;Dong-Soo Kim
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.25-29
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    • 1978
  • Cobalt(III) complex containing ethylenediamine-triacetate and trimethylenediamine has been isolated from the reaction of ethylenediamine-tetraacetatocobaltate(III) with trimethylene-diamine in aqueous solution by Dowex 50W-X8, cation exchange resin in $H^+$ form. The ethylenediamine-triacetate($EDTRA^{3-}$) ligand coordinates to the cobalt(III) ion as a quadridentate with a free acetate branch. It has been observed that the complex has trans(O-O) (1) structure via the elemental analysis, UV, IR and NMR data.

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The Stereochemistry of the Metal Complexes of Novel Stereospecific Quadridentate Ligands, Cobalt(Ⅲ) Complexes of N,N$^\prime$-dimethylethlenediamine-N,N$^\prime$-di-$\alpha$-propionato and N,N$^\prime$-dimethlethylenediamine-N,N$^\prime$-diacetato Ligands

  • Jun, Moo- Jin;Jung, Jin- Seung;Kim, Chang-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.6 no.6
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    • pp.369-374
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    • 1985
  • A new flexible quadridentate ligand, N,N'-dimethylethylenediamine-N,N'-di-${\alpha}$-propionic acid (dmedpa) has been synthesized, and diammine and ethylenediamine cobalt(III) complexes of dmedpa, $[Co(dmedpa)(NH_3)_2]^+$ and $[Co(dmedpa(en)]^+,$ have been prepared. Only s-cis isomer has been yielede. A known N,N'-dimethylethylediamine-N,N'-diacetic acid (dmedda) has also been prepared. Dichloro cobalt(III) complexes of both dmedda and dmedpa have been prepared. Only the s-cis isomer has been yielded in the $[Co(dmedda)Cl_2]^-$ complex, while only the uns-cis isomer has been obtained for the $[Co(dmedpa)Cl_2]^-$ complex.

Selective Oxidation of 2,6-di-tert-butylphenol and Electrochemical Properties by Oxygen Adducted Tetradentate Schiff Base Cobalt (Ⅲ) Activated Catalysts in Aprotic Solvents (비수용매에서 산소 첨가된 네자리 Schiff Base Cobalt(Ⅲ) 활성 촉매들에 의한 2,6-di-tert-butylphenol의 선택 산화와 전기화학적 성질)

  • Jo, Gi Hyeong;Choe, Yong Guk;Ham, Hui Seok;Kim, Sang Bok;Seo, Seong Seop
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.569-581
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    • 1990
  • It is generated in DMF by activated catalysts of superoxo cobalt(III) complex, such as [Co(III)(Schiff base)(L)]O$_2$ (Schiff base; SED, SOPD and o-BSDT, L; DMF and Py) which mole ratio of oxygen to metal is 1:1 that oxidation major product of 2,6-di-tert-butylphenol by homogeneous oxidatve catalysts of oxygen adducted tetradentate Schiff base cobalt(III) is 2,6-ditert-butylbenzoquinone (BQ). And oxidation product of 3,3',5,5'-tetra-tert-butyldiphenoquinone (DPQ) is generated by activated catalysts such as $\mu$-peroxo cobalt(III) complex; $[Co(III)(SND)(L)]_2$$O_2$ (L; DMF and Py) which mole ratio of oxygen to metal is 1:2. It is difficult to identify these homogeneous activated catalysts such as superoxo and $\mu$-peroxo cobalt(III) complexes in DMF and DMSO solvents. But we can identify by P.V.T method of the oxygen absorption in pyridine solvent and by the reduction process occurred to four steps including prewave of O$_2$- in 1:1 oxygen adducted superoxo cobalt(III) complexes and three steps not including prewave of O$_2$- in 1:2 oxygen adducted $\mu$-peroxo cobalt(III) complexes by the cyclic voltammetry with glassy carbon electrode in 0.1 M TEAP as supporting electrolyte solutidn.

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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.

Light-Induced Electron Transfer Reactions in FeⅡ-CoⅢ Binuclear Complexes ($Fe^{II}-Co^{III}$이핵착물의 광유발 전자이동반응)

  • Lee, Gyu Hwan
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.598-602
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    • 1994
  • Light-induced electron transfer reaction within binuclear complex $(NC)_5FeII-L-CoIII(NH_3)_5$ was studied with steady-state photolysis and the rate constants were measured for various bridging lignands. klight and quantum yields for BP, PHEN, DAP having conjugation between metal binding sites were about $3{\times}10^{-2} sec^{-1}$ and 1, and for BPEA having no conjugation were about $2{\times}10^{-4} sec^{-1}$ and 0.03. Light-induced electron transfer reaction within binuclear complex was proved to be the chemical mechanism which had charge transfer excited state MLCT*.

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Cyanide-bridged Trinuclear and Ethylenediamine-bridged One-dimensional Cobalt(III)-Manganese(II) Complexes: Synthesis, Crystal Structures and Magnetic Properties

  • Zhang, Daopeng;Zhang, Lifang;Zhao, Zengdian;Ni, Zhonghai
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2544-2548
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    • 2011
  • Two pyridinecarboxamide cobalt dicyanide building blocks and Mn(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three trinuclear cyanide-bridged $Co^{III}-Mn^{II}$ complexes: $\{[Mn(MeOH)_4][Co(bpb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (1), $\{[Mn(MeOH)_4][Co(bpmb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (2) and $\{[Mn(DMF)_2(en)_2][Co(bpb)(CN)_2]_2\}{\cdot}2DMF{\cdot}H_2O$ (3) ($bpb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, en = ethylenediamine). Single crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. For complex 3, it was further linked into one-dimensional structure by ethylenediamine acting as bridges. Investigation of the magnetic properties of complex 3 reveals weak antiferromagnetic coupling between the neighboring Mn(II) centers through the bridging ethylenediamine molecule. A best-fit to the magnetic susceptibilities of complex 3 gave the magnetic coupling constant J = -0.073(2) $cm^{-1}$.