• Journal of the Korean Chemical Society
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• v.26 no.5
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• pp.310-319
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• 1982

Cobalt(III) complexes with sexidentate ligands, N,N,N',N'-tetrakis(2-amino-ethyl)-1,2-ethanediamine (ten), -1,3-propanediamine (ttn), -1,4-butanediamine (ttmd), -(R,R)-and -(R,S)-2,4-pentanediamine (tptn) were prepared, and the characterization of d-d absorption band on the variation of chelate ring size and conformation of these complexes were studied by means of electronic spectra. The first d-d absorption bands of $[Co(L)]^{3+}$ complexes are shifted to smaller wave numbers in the order. ttn > (R,R)-tptn > ten > ttmd${\simeq}$(R,S)-tptn for (L). The UV, $^{13}C$ NMR, and Circular Dichroism studies indicate that the R,S-tptn ligand of $[Co(R,S-tptn)]^{3+}$ complex coodinates to cobalt(Ⅲ) ion as a sexidentate with one methyl group in axial position.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.84-89
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• 1986

A newflexible $N_2O_2$-type tetradentate ligand. Ethylenediamine-N,N'-di-${\alpha}$-isobutyric acid(eddib), has been synthesized, and dichloro cobalt(III) complex of eddib has been prepared via the air-oxidation technique. Only S-cis isomer has been yielded during the preparation of complex. Ring strain and steric hinderance are cited as the cause for the preference for the S-cis geometric configuration. On series of cobalt(III) complexes of eddib, $[Co(eddib)L]^{n+}$ $(L = Cl{\cdot}(H_2O),\;CO_3^{2-},\;(H_2O)_2)$have been prepared in situ. In their electronic absorption spectra, the absorption maxima and their intensities of the above series of complexes are on the ordinary line of the spectrochemical and hyperchromic series. Elemental analysis, IR, NMR and electronic absorption spectra have been used to characterize the complex and geometries of the complex.

• Journal of the Korean Chemical Society
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• v.22 no.5
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• pp.295-303
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• 1978

The dipole moments for octahedral [Co(III)-$O_3N_3$], tetrahedral [M(II)-$O_2N_2$] and square planar [M(II)-$O_2N_2$] types complexes are calculated by the expansion method for spherical harmonics using the valence basis sets for the central metal ion and the single basis set orbital ($2p_z$) for ligands. The calculated dipole moments for these complexes are in agreement with the experimental values.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.709-719
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• 1992

We synthesized the binuclear tetradentate Schiff base cobalt(II), nickel(II) and copper(II) complexes such as [Co(II)_2(TSBP)(L)_4], [Ni(II)_2(TSBP)(II)_4] and [Cu(II)_2(TSBP)] (TSBP: 3,3',4,4'-tetra(salicylideneimino)-1,1'-biphenyl, L: Py, DMSO and DMF). We identified the binucleated structure of these complexes by elemental analysis, IR-spectrum, UV-visible spectrum, T.G.A. and D.S.C. According to the results for cyclic voltammogram and differential pulse polarogram of 1 mM complexes in nonaqueous solvents included 0.1M TEAP-L (L; Py, DMSO and DMF) as supporting electrolyte, it was found that diffusionally controlled redox processes of four steps through with one electron for binucleated Schiff base Cobalt(II) complex was Co(III)_2 {^\longrightarrow \\_\longleftarrow^e^-}Co(III)Co(II)_2{^\longrightarrow \\_\longleftarrow^e^-}Co(II){^\longrightarrow \\_\longleftarrow^e^-}Co(I){^\longrightarrow \\_\longleftarrow^e^-}Co(I)_2 and two steps with one electron for Nickel(II) and Copper(II) complexes were M(II)_2 {^\longrightarrow \\_\longleftarrow^e^-}M(I)M(I){^\longrightarrow \\_\longleftarrow^e^-}M(I)_2 (M; Ni and Cu) in nonaqueous solvents.

• Journal of the Korean Chemical Society
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• v.25 no.5
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• pp.306-310
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• 1981

Induced circular dichroism spectra of racemic cobalt(III) complexes for $[Co(en)_3]^{3+},\;[Co(tn_)3]^{3+},\;cis-[Co(NH_3)(en)_2]^{3+},\;[Co({\beta}-ala)(en)2_]^{2+},\;[Co(gly)(en)_2]^{2+}\;and\;[Co(acac)(en)_2]^{2+}$ were measured when they were dissolved in aqueous d-tartrate2- solution at room temperature. Only a single negative CD spectrum was observed for all the complexes above in visible region(400∼500nm). It was interpreted that these CD bands were attributed to the difference in interaction between ${\Lambda}$-and ${\Delta}$-enantiomers with d-tartrate$^{2-}$. Namely, when d-tartrate$^{2-}$ was added to ${\Lambda}$-enantiomer and ${\Delta}$-enantiomer, it caused ${\Lambda}$-enantiomer to change greatly and ${\Delta}$-enantiomer to change only slightly; combined the results proved induced circular dichroism. The enantiomer for which the eluent has a stronger affinity should be eluted faster in ion-exchange column chromatography. It is possible to predict the elution order of chromatography from the sign of the induced CD if stronger interaction of chiral anion with the complex leads to greater change in the natural CD spectrum of the complex. The elution order was in complete agreement with the prediction from the sign of the induced CD spectrum for all the measured complexes.

• 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.46 no.3
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• pp.219-224
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• 2002

The oxidation reaction between 2,6-di-tert-butylphenol (DTBP) and oxygen adducted Co(III) complexes as a catalysis has been studied by UV-visible spectrophtometry. According to the results, main product is 2,6-di-tert-butylbenzoquinone(BQ) and the activity of the complexes is bigger in [Co(III)2(SMPD)2(Py)2]2O2 than in [Co(III)2(SPPD)2(Py)2]2O2. The rate constant is 4.55~2.12${\times}$10$-3}$s. It was found that the oxidation reaction is primary reac-tion or concentration of catalysis, O2 molecule and substance. The reasult is far from Arrhenius properties because acti-vationenergy is 10.38 kJ/mol.

• 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.

• 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.