• Journal of the Korean Chemical Society
• /
• v.32 no.2
• /
• pp.122-129
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.21 no.12
• /
• pp.1271-1273
• /
• 2000

• Journal of the Korean Chemical Society
• /
• v.49 no.3
• /
• pp.329-333
• /
• 2005

• Journal of the Korean Chemical Society
• /
• v.34 no.6
• /
• pp.569-581
• /
• 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
• /
• v.36 no.5
• /
• pp.709-719
• /
• 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
• /
• v.33 no.2
• /
• pp.215-224
• /
• 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.

• Journal of the Korean Chemical Society
• /
• v.36 no.3
• /
• pp.428-441
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.4
• /
• pp.829-834
• /
• 2010

Ligand variation was carried out on a cobalt(III) complex of Salen-type ligand comprised of 1,2-cyclohexenediamine and salicylaldehyde bearing a methyl substituent on 3-position and -[$CMe(CH_2CH_2CH_2N^+Bu_3)_2$] on 5-position, which is a highly active catalyst for $CO_2$/propylene oxide copolymerization. Replacement of the methyl substituent with bulky isopropyl group resulted in alteration of the binding mode, consequently lowering turnover frequency significantly. Replacement with an ethyl group preserved binding mode and activity. Replacement of the tributylammonium unit with trihexylammonium or trioctylammonium, or replacement of 1,2-cyclohexenediamino unit with -$NC(Me)_2CH_2N$- decreased activity, even though the binding mode was unaltered.

• Bulletin of the Korean Chemical Society
• /
• v.13 no.6
• /
• pp.659-662
• /
• 1992

The pressure-jump relaxation method has been used to determine the rate constants for the formation and dissociation of maganese(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) with some dicarboxylates in aqueous solution at zero ionic strength. The carboxylate ligands used are 3-nitrophthalate, 4-nitrophthalate, and phenylmalonate. The activation parameters have alse been obtained from the temperature dependence of the rate constants. A dissociative interchange mechanism with a chelate ring closure step as rate determining is employed to interpret the kinetic data of manganese(Ⅱ) and cobalt(Ⅱ) complexes. The rates of formation of nickel(Ⅱ) complexes are controlled by both the solvent exchange step and the chelate ring closure step.

• Bulletin of the Korean Chemical Society
• /
• v.11 no.4
• /
• pp.354-357
• /
• 1990

Synthesis of dichloro cobalt (Ⅲ) complexes of a flexible $N_2O_2-type$ tetradentate ligand, ethylenediamene-N,N'-di-${\alpha}$-isobutyric acid (eddib), has yielded two geometrical isomers, s-cis-$(Co(eddib)Cl_2)- and uns-cis-(Co(eddib)Cl_2)-.$ A series of substitution reactions, $(Co(eddib)Cl_2)^- {\to} (CO(eddib)Cl H_2O) {\to} (Co(eddib)CO_3)^- {\to} (Co(eddib(H_2O)_2)^+$ have been run for each of the two geometrical isomers. The reaction between the s-cis-(Co(eddib)Cl_2)^-$ complex and L-alanine (L-als) or S-methyl-L-cysteine (L-mcy) gave the meridional s-cis-[Co(eddib)(aa)) (aa = L-ala or L-mcy) complex. The S-methyl-L-cysteine was found to coordinate to cobalt (Ⅲ) ion via the nitrogen and oxygen donor atoms.