• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.541-542
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• 2009

• Bulletin of the Korean Chemical Society
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• v.21 no.4
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• pp.405-411
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• 2000

Electrochemical and spectroelectrochemical studies of cobalt-Schiff (Co-SB) base complexes, Co(salen) [N-N'-bis(salicylaldehyde)-ethylenediimino cobalt(II)] and Co(salophen) [N-N'-bis(salicylaldehyde)-1,2-pheny-lenediimino cobalt(II)], have been c arried out to test them as oxygen reduction catalysts. Both compounds were found to form an adduct with oxygen and exhibit catalytic activities for oxygen reduction. Comparison of spec-tra obtained from electrooxidized complexes with those from Co-SB complexes equilibrated with oxygen in-dicates that the latter are consistent with the postulated complex formed with oxygen occupying the coaxial ligand position, namely, Co(III)-SB·O2 - .The catalysis of oxygen reduction is thus achieved by reducing Co(III) in the oxygen-Co-SB adduct, releasing the oxygen reduction product, e.g., O2 - ., from the Co(II)-SB complex.

• Applied Chemistry for Engineering
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• v.20 no.3
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• pp.279-284
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• 2009

The formation of mesoporous pores in the microporous mordenite crystals was performed by controlled silica extraction on alkaline treatment. Inner tunable mesopore size could be controlled by changing the concentration of alkaline solution. The pore structure of mordenite zeolite was studied by instrumental analysis after alkaline-treatment. To obtain the cage type mesopores, Ti-coating on the ourside mordenite crystals before alkaline treatment was investigated to be the most effective. Polymeric chiral salen Co (III) complexes were successfully encapsulated in mesoporous mordenite zeolite by "ship-in-a-bottle" method. The heterogeneous catalyst could be applied in asymmetric ring opening of epichlorohydrine by water. It showed very excellent enantioselectivity with a high yield in the catalysis.

• Applied Chemistry for Engineering
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• v.18 no.6
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• pp.562-567
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• 2007

The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their use as versatile starting materials as well as chiral intermediates. In this study, new polymeric chiral Co(salen) complexes bearing tallium (III)chloride and iron (III)chloride (ferric chloride) have been synthesized and characterized. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides using water and phenol derivatives as nucleophiles. The easily prepared polymeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ and phenol nucleophiles, providing enantiomerically enriched terminal epoxides (> 98% ee). The system described in this work is very efficient for the synthesis of chiral epoxide, 1,2-diol and ${\alpha}$-aryloxy alcohol intermediates.

• Applied Chemistry for Engineering
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• v.27 no.5
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• pp.490-494
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• 2016

This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).

• Korean Chemical Engineering Research
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• v.43 no.6
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• pp.647-661
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• 2005

The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this review, we investigate the research and development trend in the asymmetric ring opening reactions using cobalt salen catalysts. Hydrolytic kinetic resolution (HKR) technology is the very prominent way to prepare optically pure terminal epoxides among available methods. We have synthesized homogeneous and heterogeneous chiral dinuclear salen complexes and demonstrated their catalytic activity and selectivity for the asymmetric ring opening of terminal epoxides with variety of nucleophiles and for asymmetric cyclization to prepare optically pure terminal epoxides in one step. The resolved ring opened product combined with ring closing in the presence of base and catalyst afforded the enantioriched terminal epoxides in quantitaive yield. Potentially, these catalysts are using on an industrial scale to produce chiral intermediates. The experimental results of HKR technology applied to the synthesis of various chiral compounds are presented in this paper.

• Journal of Electrochemical Science and Technology
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• v.9 no.3
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• pp.169-175
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• 2018

Cu-Salen complex was prepared and attached into chitosan (Cs) polymer backbone. Nanocomposite of the synthesized polymer was prepared with functionalized carbon nano-particles (Cs-Cu-sal/C) to modify the electrode surface. The surface morphology of (Cs-Cu-sal/C) nanocomposite film showed a homogeneous distribution of carbon nanoparticles within the polymeric matrix. The cyclic voltammogram of the modified electrode exhibited a redox behavior at -0.1 V vs. Ag/AgCl (3 M KCl) in 0.1 M PB (pH 7) and showed an excellent hydrogen peroxide reduction activity. The Cs-Cu-sal/C electrode displays a linear response from $5{\times}10^{-6}$ to $5{\times}10^{-4}M$, with a correlation coefficient of 0.993 and detection limit of $0.9{\mu}M$ (at S/N = 3). The sensitivity of the electrode was found to be $0.356{\mu}A\;{\mu}M^{-1}\;cm^{-2}$.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.355-362
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• 2009

The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized oxovanadium(IV) Schiff-base; N,N'-bis(4-hydroxysalicylidene)-ethylene-1, 2-diamineoxovanadium(IV), [VO($(OH)_2$-salen)]; has been covalently anchored on modified MWNTs. The new modified MWNTs ([VO($(OH)_2$-salen)]-MWNTs]) have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), UV-Vis, Diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The analytical data indicated a composition corresponding to the mononuclear complex of tetradentate Schiff-base ligand. The characterization of the data showed the absence of extraneous complex, retention of MWNTs and covalently anchored on modified MWNTs. Liquid-phase oxidation of cyclohexane with $H_2O_2$ to a mixture of cyclohexanone, cyclohexanol and cyclohexane-1,2-diol in $CH_3$CN have been reported using oxovanadium(IV) Schiff-base complex covalently anchored on modified MWNTs as catalysts. This catalyst is more selective toward cyclohexanol formation.

• Applied Chemistry for Engineering
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• v.25 no.5
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• pp.503-509
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• 2014

The carbon/porous silica composite membrane was fabricated in a simple manner, which could be successfully for the simultaneous separation and production of chiral epoxides and 1,2-diols, based on their differences in hydrophilic/hydrophobic natures. The chiral Co(III)-$BF_3$ salen catalyst adopted in the membrane reactor system has given the very high enantioselectivity and recyclability in hydrolysis of terminal epoxides such as ECH, 1,2-EB, and SO. The optically pure epoxide and the chiral catalyst were collected in the organic phase after hydrolysis reaction. The hydrophilic water-soluble 1,2-diol product hydrolyzed by chiral salen diffused into the aqueous phase through the SBA-16 or NaY/SBA-16 silica composite layer during the reaction. The water acted simultaneously as a reactant and a solvent in the membrane system. One optical isomer was obtained with high purity and yield, and furthermore the catalysts could be recycled without observable loss in their activity in the continuous flow-type membrane reactor.

• Applied Chemistry for Engineering
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• v.30 no.3
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• pp.365-370
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• 2019

In this study, effects of the ultrasonic irradiation during the reaction process were investigated for the enantioselective kinetic resolution (EKR) reaction of racemic epoxides in the presence of chiral cobalt salen catalysts, as compared to that of using the conventional mechanical stirring. In order to compare catalytic activities, the chiral cobalt salen complexes having $AlCl_3-$, $BF_3-$ and nitrobenzenesulfonic acid (NBSA) were synthesized and used as catalysts, and then three kinds of the racemic epoxides such as ephichlorohydrine (ECH), epoxy phenoxypropane (EPP) and propylene oxide (PO) were used as reactants. In addition, EKR reactions have been performed using the water and methanol as nucleophiles, respectively. The unique contribution of ultrasonic irradiation as a powerful mixing medium was evaluated in this study to improve the kinetics in comparison to the conventional mechanical agitation during EKR reactions. The reaction time to obtain the highest 99 ee% became shorten more than that of above 60%, when the ultrasonic irradiation was used. This result may be interpreted by the cavitation effect of ultrasound in the solution, generating a powerful shear force for the very violent mixing.