• 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 $$[Co(III)_2-O_2-CO(III)]\rightarrow^{e^-}[Co(III)-O_2-Co(II)]\rightarrow^{e^-}[Co(II)-O_2-Co(II)]\rightleftarrows^{e^-}[Co(II)+Co(II)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(II)+Co(I)+O_2{\cdot}^-]\rightleftarrows^{e^-}[Co(I)+Co(I)+O_2{\cdot}^-]$$.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.295-303
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• 1989

Tetradentate Schiff base cobalt(II) complex; Co(SND) and Co(SOPD) were synthesized, and these complexes were allowed to react with dry oxygen to form oxygen adducts cobalt(III) complexes such as $[Co(SND)(Py)]_2O_2$ and $[Co(SOPD)(Py)]_2O_2$ in pyridine. These complexes have been identified by IR specta, T.G.A., magnetic susceptibilities measurements and elemental analysis. It has been found that the oxygen adducts coblat(III) complexes have hexacoordinated octahedral configuration with tetradentate Schiff base cobalt(II), pyridine and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1;2. The redox reaction processes of $Co(SND)(Py)_2$ and $Co(SOPD)(Py)_2$ complexes were investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP pyridine. The result of redox reaction processes of Co(III)/Co(II) and Co(II)/Co(I) for $Co(SND)(Py)_2$ and $Co(SOPD)(Py)_2$ complexes are reversible or quasi reversible process but oxygen adducts complexes are irreversible processes. Redox process for oxygen of oxygen adducts complexes was quasi reversible and redox range of potential was $E_{pc}\;=\;-0.96{\sim}-1.03V$ and $E_{pa}\;=\;-0.78{\sim}-0.80V.$

• 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.

• 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.

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.51-62
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• 1990

Pentadentate Schiff base cobalt(II) complexes; Co(II)(Sal-DET) and Co(II)(Sal-DPT) were synthesized and these complexes were allowed to react with dry to form oxygen adducts of cobalt(II) complexes such as [Co(III)(Sal-DET)]$_2O_2$ and [Co(III)(DPT)]$_2O_2$ in aprotic solvents. These complexes have been identified by IR spectra, TGA, DSC, magnetic susceptibility measurements, and elemental analysis. It has been found that the oxygen adadduct complexes of $\mu$-peroxo type have hexaccordinated octahedral configuration with pentadentate schiff base cobalt(II) and oxygen, but the mole ratio of oxygen to cobalt(III) complexes of first step for oxygen adduct formation reaction of cobalt(II) complexes in aprotic solvents are 1:1. The redox reaction processes of Co(II)(Sal-DET), Co(II)(Sal-DPT), and oxygen adduct of cobalt(II) complexes were investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine. As a result the reduction reaction processes of Co(III)/Co(II) and Co(II)/Co(I) for cobalt(II) complexes and oxygen adducts of cobalt(II) complexes are two irreversible steps of one eletron process, and reaction processes of oxygen for oxygen adducts complexes were quasireversible and redox range of potential was $E_{pc}$ = -0.97V∼-0.86V and $E_{pa}$ = -0.87V ∼ 0.64V.

• 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.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.509-519
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• 1987

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.422-431
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• 1998

Tridentate Schiff base ligands such as $SIPH_2,\;SIPCH_2,\;HNIPH_2,\;and\; HNIPCH_2$ were prepared by the reaction of salicylaldehyde and 2-hydroxy-l-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. The structures and properties of ligands and their Co(II) complexes were investigated by elemental analysis, $^1H$NMR, IR, UV-visible spectra, and thermogravimetric analysis. The molar ratio of Schiff base to the metal of complexes was found to be 1:1. Co(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 a supporting electrolyte were investigated by cyclic voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Co(II) complexes were irreversible and one electron processes by two steps in diffusion controlled reaction. The reduction potential of the Co(II) complexes was shifted to the positive direction in the order [Co(Ⅱ)$(HNIPC)(H_2O)_3$]>[Co(Ⅱ)$(HNIP)(H_2O)_3$]>[Co(II)$(SIPC)(H_2O)_3$]>[Co(Ⅱ)$(SIP)(H_2O)_3], and their dependence on ligands were not so high.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.719-725
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• 1998

Tridentate Schiff base ligands were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. And then Cu(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. Cu(II) complexes were contemplated to be four-coordinated square planar configuration containing one water molecule. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a 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 Cu(II) complexes was quasi-reversible and diffusion-controlled as one electron by one step process Cu(II)/Cu(I). The reduction potentials of the Cu(II) complexes shifted in the positive direction in the order of [Cu(II)(HNIPC)($H_2O$)]>[Cu(II)(HNIP)($H_2O$)]>[Cu(II)(SIP)($H_2O$)]>[Cu(II)(SIPC)($H_2O$)].

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.261-272
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• 1992

Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.