• Bulletin of the Korean Chemical Society
• /
• v.24 no.6
• /
• pp.829-831
• /
• 2003

Various theoretical studies of σ-bond activation of organic molecules by transition metal complexes arereviewed. In the homolytic σ-bond activation, the d orbital energy level of the central metal is an importantfactor, as well known. At the same time, the electron-withdrawing substituent which stabilizes the sp3 orbitalaccelerates the homolytic σ-bond activation. In the heterolytic C-H σ-bond activation of RH by $MXL_n$, the XHbond formation is an important driving force, where $MRL_n$ and HX are formed as products. The heterolytic σ-bond activation is also understood in terms of the electrophilic attack of the metal center to the substrate.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.5
• /
• pp.1421-1423
• /
• 2010

• Journal of the Korean Chemical Society
• /
• v.8 no.1
• /
• pp.20-24
• /
• 1964

The linear combination of bond orbitals method is used to investigate the reactivity of halomethanes in abstraction reactions by atoms. The activation energy is evaluated on the assumption that, in an activated complex, two electrons in a bond to be broken become completely isolated from the rest of the ${\sigma}$-electron systems. Such a model leads to an intuitively attractive concept that the interactions between the reactive bond and the neighboring bonds govern the reactivity of ${\sigma}$-electron systems. The resulting equation for the activation energy, ${\varepsilon},\;is:\;{\narepsilon}= ${\varepsilon}={\zeta}+$$${\sum}_{i=1}^3$${\eta}c-I,$ c-4 Here, subscript C-4 indicates the bond to be broken, while C-i represents the other three bonds surrounding the reactive bond; ξ is the activation energy of a hypothetical reaction of an isolated C-4 bond and an attacking atom; and ${\eta}$C-i,C-4 stems from the stabilizing interacting of C-4 bond with neighboring C-i bonds. A choie of η′s consistent with bond strength data simplifies the above equation to a form ${\varepsilon}={\zeta}\;+\;N{\eta}c$-H, C-4 where N denotes the number of C-H plus C-F bond in halomethanes. In agreement with this equation, experimental -values increase linearly with increasing N.

• Journal of the Korean Chemical Society
• /
• v.19 no.1
• /
• pp.11-15
• /
• 1975

Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.12
• /
• pp.1122-1124
• /
• 1994

• Journal of the Korean Chemical Society
• /
• v.9 no.1
• /
• pp.23-28
• /
• 1965

Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

• Journal of the Korean Chemical Society
• /
• v.13 no.4
• /
• pp.297-302
• /
• 1969

The activation parameters for the nucleophilic addition reactions of n-propyl-, n-butyl-, n-amyl-and n-hexyl-mercaptan to 3, 4-methylene-dioxy-${\beta}$-nitrostyrene were determined at pH 5.8 and pH 2.0, and also the isokinetic temperature of the reactions at pH 5.8 was obtained numerically 262${\circ}$K, and at pH 2.0, 17.1${\circ}$K. From the values obtained above, the fact that the mercaptan having the longer carbon chain has the greater nucleophilicity of it in the addition reactions has been discussed by the extrathermodynamic analysis of ${\Delta}H^{\neq}$and ${\Delta}S^{\neq}$.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.4
• /
• pp.953-958
• /
• 2010

A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within $Ti^+(CH_3COCH_3)_n$ heterocluster ions. The reactions of $Ti^+$ with $CH_3COCH_3$ clusters were found to be dominated exclusively by an oxidation reaction, which produced $TiO^+(CH_3COCH_3)_n$ clusters. These ions were attributed to the insertion of a $Ti^+$ ion into the C=O bond of the acetone molecule within the heteroclusters, followed by $C_3H_6$ elimination. The mass spectra also indicated the formation of minor sequences of heterocluster ions with the formulas $Ti^+(C_3H_4O)(CH_3COCH_3)_n$ and $TiO^+(OH)(CH_3COCH_3)_n$, which could be attributed to C-H bond insertion followed by $H_2$ elimination and to the sequential OH abstraction by the $TiO^+$ ion, respectively. Density functional theory calculations were carried out to model the structures and binding energies of both the association complexes and the relevant reaction products. The reaction pathways and energetics of the $TiO^+\;+\;CH_2CHCH_3$ product channel are presented.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2009.05a
• /
• pp.29.1-29.1
• /
• 2009

Fabrication of good quality P-type GaN remained as a challenge for many years which hindered the III-V nitrides from yielding visible light emitting devices. Firstly Amano et al succeeded in obtaining P-type GaN films using Mg doping and post Low Energy Electron Beam Irradiation (LEEBI) treatment. However only few region of the P-GaN was activated by LEEBI treatment. Later Nakamura et al succeeded in producing good quality P-GaN by thermal annealing method in which the as deposited P-GaN samples were annealed in N2 ambient at temperatures above $600^{\circ}C$. The carrier concentration of N type and P-type GaN differs by one order which have a major effect in AlGaN based deep UV-LED fabrication. So increasing the P-type GaN concentration becomes necessary. In this study we have proposed a novel method of activating P-type GaN by electrochemical potentiostatic method. Hydrogen bond in the Mg-H complexes of the P-type GaN is removed by electrochemical reaction using KOH solution as an electrolyte solution. Full structure LED sample grown by MOCVD serves as anode and platinum electrode serves as cathode. Experiments are performed by varying KOH concentration, process time and applied voltage. Secondary Ion Mass Spectroscopy (SIMS) analysis is performed to determine the hydrogen concentration in the P-GaN sample activated by annealing and electrochemical method. Results suggest that the hydrogen concentration is lesser in P-GaN sample activated by electrochemical method than conventional annealing method. The output power of the LED is also enhanced for full structure samples with electrochemical activated P-GaN. Thus we propose an efficient method for P-GaN activation by electrochemical reaction. 30% improvement in light output is obtained by electrochemical activation method.

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