• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.221-224
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• 2002

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to ethyl-${\alpha}$-cyanocinnamates (ECC;$YC_6H_4CH$=C(CN)COOEt) have been investigated in acetonitrile at $30.0^{\circ}C$. The rate is first order with respect to BA and ECC. The rate is slower than that expected from the additive effect of ${\sigma}^-$ or $R^-$ for the activating groups (CN and COOEt). Natural. bond orbital ${\pi}^{\ast}_{c=c}$ calculations show that the contribution of COOEt group may not be fully effective despite the coplanar molecular structure. The selectivity parameters including the cross-interaction constant (${\rho}_{xy}$ = -0.22) indicate that the addition occurs in a single step. The kinetic isotope effects ($k_H/k_D$=2.5-2.8) involving deuterated BA ($XC_6H_4CH_2ND_2$) nucleophiles and activation parameters (${\Delta}H^{\neq}=4{\sim}6\;kcal\;mol^{-1};{\Delta}S^{\neq}=-45{\sim}-52\;e.u.$) suggest a cyclic transition state in which N-$C_{\alpha}$ and H-$C_{\beta}$ bonds are formed concurrently.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2628-2632
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• 2011

The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

• Journal of the Korean Chemical Society
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• v.18 no.6
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• pp.391-399
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• 1974

Corrosion and passivation of metallic cobalt was studied by means of electrochemical experiments including potentiostatic and galvanostatic measurements and cyclic voltammograms. The mechanisms of active dissolution and passivation of cobalt at the metal/borate buffer solution interface are deduced from the Tafel slope, pH dependence of the Flade potential, and dissolution kinetic data. Hydroxyl group adsorbed on cobalt surface seems to participate in surface oxidation and formation of the passive layer. The growth kinetic data as measured by the current density suggests a mechanism in which the growth of the passive layer is determined by field-assisted transport of ions through the layer. Thickness of the passive layer was estimated by coulometry to be about 10${\AA}$ at the lowest passive potential and to grow gradually with anodic potential to about 20${\AA}$.

• Journal of the Korean Chemical Society
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• v.29 no.6
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• pp.623-628
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• 1985

Rate constants for complexing with thiocyanate after ring opening of molybdenum-oxalate in acid media were obtained spectrophotometrically at 460nm. The acid-assisted dissociation of molybdenum-oxalate and the reaction of thiocyanate with oxalatooxomolybdenum (V) complex in acid media were investigated with thiocyanate and hydrogen ion concentration. The kinetic data indicate that molybdenum-oxalate is protonated to a limited extent in acid media and the protonated complex is responsible for an increase in rate for the reaction of thiocyanate with oxalatooxomolybdenum (V) complex. Replacement of an oxalate ligand in acid media has been interpreted in terms of dissociative mechanism involving bond-breaking of the oxygen trans to the yl oxygen.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.50-57
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• 1989

A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.510-514
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• 1991

Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.511-516
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• 1992

The catalytic oxidation of CO on perovskite $Eu_{1-x}Sr_xCoO_{3-y}$, has been investigated at reaction temperatures from 100 to $250^{\circ}C$ under stoichiometric CO and $O_2$ partial pressures. The microstructure and Sr-substitution site of the catalyst were studied by means of infrared spectroscopy. The reaction rates were found to be correlated with 1.5-and 1.0-order kinetics with and without a $CO_2$ trap, respectively; first-and 0.5-order with respect to CO and 0.5-order to $O_2$ with the activation energy of 0.37 eV $mol^{-1}$. It was found from IR, ${\sigma}$ and kinetic data that $O_2$ adsorbs as an ionic species on the oxygen vacancies, while CO adsorbs on the lattice oxygens. The oxidation reaction mechanism is suggested from the agreement between IR, ${\sigma}$ and kinetic data.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.621-625
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• 1993

Kinetic studies are conducted for the reactions of Y-benzoyl, Y-benzenesulfonyl and Y-benzyl halides with X-anilines in acetonitrile, and the transition state (TS) structures and their variations with substituents X and Y are discussed. The magnitude of the cross-interaction constants, $\rho$xy, is the largest and the inverse secondary kinetic isotope effect (SKIE), $k_H/k_D$ < 1.0, with deuterated aniline nucleophiles is the smallest for benzoyl fluoride reflecting the tightest TS for this compound. The SKIEs for sulfonyl halides are relatively large due to a relatively large, diffuse nature of the reaction center, S, causing weaker steric hindrance to the vibrations of the two N-H(D) bonds. For benzoyl and sulfonyl halides, the trends in $k_H/k_D$ and $Ir_XI$ variations with $\sigma$Y contradict each other, which is rationalized by the negative charge accumulation on the reaction center, CO and SO$_2$, causing inefficient transfer for the substrate with an electron donating substituent.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.281-286
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• 1990

The kinetics and mechanism of reduction of Cu(II) with an excess D-penicillamine have been examined at pH = 6.2 and 0.60M in ionic strength. The reaction at the initial stage is biphasic with a rapid complexation process to give "red" transient complex of $[Cu(II)(pen)_2]^2$- that is partially reduced to another transient "brown" intermediate. The "brown" intermediate is finally reduced to diamagnetic "yellow" complex, $[Cu(I)(Hpen)]_n$. The final reduction process is pseudo-first order in ["brown" transient] disappearance $with {\kappa} = {{\kappa}_{3a} + {\kappa}_{3b}[pen]^{2-}},$ where ${\kappa}_{3a} = (5.0{\pm}0.8){\times}10^{-3}sec^{-1}$ and ${\kappa} = (0.14{\pm}0.02) M^{-1}sec^{-1}$ at $25^{\circ}C$. The activation parameters for the $[H_2pen]$-independent and $[H_2pen]$-dependent paths are ${\Delta}H^{\neq} = (52{\pm}5)kJmol^{-1},$ and ${\Delta}S^{\neq} = ( - 27{\pm}3)JK^{-1}mo^{l-1},$ and ${\Delta}H^{\neq} = (56{\pm}2)kJmol^{-1}$ and ${\Delta} S^{\neq} = ( - 18{\pm}0.7)JK^{-1}mol^{-1}$ respectively. The nature of "brown" intermediate is not clearly identified, but this intermediate seems to be in the mixed-valence state, judging from the kinetic and spectroscopic informations.