• Journal of the Korean Chemical Society
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• v.17 no.2
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• pp.95-104
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• 1973

Ground electronic structures and SNreactivities of a series of alkylchlorides (methyl,ethyl, iso-propyl, trans n-butyl, sec-butyl, tert-butylchloride) have been studied using approximate $({\sigma}-MO)$ method, such as EHT and CNDO/2. It was found that CNDO/2 gives better results for the systems such as alkylchlorides whose structural differences are not remarkable, in comparison with EHT method. According to CNDO/2 results, calculated dipole moments for alkylchlorides are slightly higher than observed values, showing the order of primary < secondary < tertiary alkylchlorides. It was also found that highest occupied(HO) MO's are completely or nearly degenerate, and show relatively weak $\pi$-antibonding nature between$\alpha$-carbon and Cl atoms. Furthermore, the electrons in this MO are largely confined to Cl atom, and hence these behaves as likely as p-lone pair electrons of Cl atom. On the contrary, lowest unoccupied (LU) MO's show strong $\sigma$-antibonding nature between $\alpha$-carbon and Cl atoms whose electron clouds are directed along the C-Cl axis. It has been discussed that the$S_N2$ reactivities of alkylchlorides may largely be controlled by ${\sigma}^{\ast}$ LUMO, and the antibonding strength between $\alpha$-carbon and Cl atoms in this MO may become the measure of $S_N2$reactivity. The relationship between $S_N2$reactivity and C-Cl bond polarizability has also been discussed. It has been suggested that the unique structure factors determining $S_N1$reactivities may be $\pi$-antibonding strength between $\alpha$-carbon and Cl atoms in HOMO and C-Cl bond strength in ground state.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.3-15
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• 1992

Electronic structures and reactivities of the chromium, molybdenum, and tungsten carbene complexes, $(CO)_5Cr=CCHCH_2(XCH_3)\;,\;(CO)_5Mo=CCHCH_2(XCH_3)\;, and\;(CO)_5W=CCHCH_2(XCH_3)$, are studied by means of Extended Huckel calculations. The origin of the M=Ccarbene double bond is clarified from the diagram of the orbital correlation with the fragment orbitals. The ${\sigma}$ bond of the M=Ccarbene double bond is formed by the electron transfer interaction from the HOMO of the carbene to the LUMO of the $(CO)_5M$. The ${\pi}$ bond is formed through the back-transfer of electrons from one of the degenerated d${\pi}$ orbitals to the LUMO of the carbene. The polarization of charge of the M=Ccarbene bond is calculated to be M=Ccarbene for Mo, and W carbenes. The chemical and physical properties of these complexes are resulted from an appreciable positive charge on the carbene carbon. The electrophilic reactivity of the carbene carbon is not charge controlled, but is controlled by the frontier orbital, LUMO.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.20 no.2
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• pp.80-84
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• 2010

The temperature-programmed reduction of titanium oxide ($TiO_2$) with pure $CH_4$ was used for the preparation of titanium carbide crystallites. The synthesized materials had the different surface areas, indicating that the structural properties of these materials were strong functions of two different heating rates and space velocity employed. The titanium carbide crystallites were active for $NH_3$ decomposition. Since the reactivity varied with changes in the particle size, ammonia decomposition reactivity over the titanium carbides crystallites appeared to be related to the different active species. The reactivities of titanium carbide crystallites were two and three times lower than those of the vanadium and molybdenum carbide crystallites, respectively. These results suggested that the difference in activities might be related to the degree of electron transfer between metals and carbon.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.266-266
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• 2012

Ni films with a thickness of 700-800 nm were deposited on carbon fiber layers using electroless deposition, and surface structures and chemical properties of these films with various annealing temperatures (300, 600 and $900^{\circ}C$) were studied. $600^{\circ}C$-annealing under atmospheric conditions resulted in formation of porous surface structures with a mean pore size of ~100 nm, whereas the other samples showed non-porous surface structures. $600^{\circ}C$-annealed Ni film showed much higher reactivities for toluene adsorption and CO oxidation comparing to other non-porous surfaces.

• Journal of the Korean Applied Science and Technology
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• v.2 no.2
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• pp.25-30
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• 1985

The transesterification reaction between diethanolamine and dimethylphthalate was kinetically investigated in the presence of various metal acetate catalysts at $130^{\circ}C$. The reaction was followed by the measurement of distilled methanol from the reaction vessel. The transesterification was found to obey first-order kinetics with respect to the concentration of diethanolamine and dimethylphthalate and catalyst, respectively. The reactivities has highest value where the electronegativity and instability constand (Kij) values for the metal acetate catalysts are about 1.6.

• Journal of the Korean Chemical Society
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• v.37 no.2
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• pp.220-227
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• 1993

Silaethene $Cl_2$Si=$CHCH_2^tBu$, generated as a metastable reaction intermediate by the thermal eliminatio of LiCl from lithiated compound $Cl_2$Si=$CHCH_2^tBu$, react with propene, 2-methylpropene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and anthracene to give ene-reaction product, 2+2-, and 2+4-cycloadducts. They are isolated by vacuum fractional distillation method and spectroscopically identified.

• Journal of the Korean Chemical Society
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• v.23 no.5
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• pp.286-295
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• 1979

In order to predict the effect of Lewis acid catalysis on the regioselectivity of the Diels-Alder reactions between unsymmetrically substituted dienes and dienophiles, the frontier orbital theory applied to the theoretical model of the Lewis acid complexed dienophile was studied by means of CNDO/2 MO. In the majority of reactions, CNDO/2 calculations gave good results in accordance with experimental orientation. Also, it was shown that the secondary orbital interaction played an important role in the regioselectivity of the Diels-Alder reaction between unsymmetrically substituted dienes and dienophiles. Although ANH's treatment is mathematically simpler than other methods, ANH's method which laid emphasis on dissymmetrical transition state gave good results on decision of regioselectivity.

• Journal of the Korean Chemical Society
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• v.23 no.5
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• pp.277-285
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• 1979

CNDO/2 calculations on $XC_6H_4CH_2Cl,\;where\;X = H,\;p-CH_3,\;p-NH_2\;and\;p-NO_2$, and on benzyl radicals, cations and anions have been carried out in order to investigate nonlinear Hammett behavior. Main conclusions reached are: 1. Benzyl chloride exhibits borderline behavior due to ${\sigma}-{\pi}$ conjugation between C-Cl bond and the ring-system. 2. The extent of mutual conjugation can be judged by $\pi$-charge and bond alternation and interfrontier level separation narrowing effects. 3.The electron donating para substituent reduces the HOMO AO coefficient of the benzylic carbon, while the electron withdrawing para substituent reduces the LUMO AO coefficient of the benzylic carbon.

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.349-357
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• 1979

A non-Boltzman equilibrium population of $Cl(^2P_{1/2})$ atoms has been observed in a flow discharge-atomic absorpion experiment. The rates of reactions of $Cl(^2P_{3/2})$ atoms with various substrates are in reasonable agreement with reported values determined by competition methods. The similar reactivities of both $Cl(^2P_{1/2})$ and $Cl(^2P_{3/2})$ atoms indicate that the contribution of $Cl(^2P_{1/2})$ atoms to the rate measurements in the competition experiment is small, and this negligible contribution may be the reason why the rate constants obtained by assuming single reactive species (in competition method) agree well with our direct measurement.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.267-270
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• 2002

Photodissociations of o-, m-, and p-iodotoluene radical cations were investigated by using Fourier-transform ion cyclotron resonance (FT-ICR) spectrometry. Iodotoluene radical cations were prepared in an ICR cell by a photoionization charge-transfer method. The time-resolved one-photon dissociation spectra were obtained at 532 nm and the identities of $C_7H_7^+$ products were determined by examining their bimolecular reactivities toward toluene-$d_8$. The two-photon dissociation spectra were also recorded in the wavelength range 615-670 nm. The laser power dependence, the temporal variation, and the identities of $C_7H_7^+$ were examined at 640 nm. The mechanism of unimolecular dissociation of iodotoluene radical cations is elucidated: the lowest barrier rearrangement channel leads exclusively to the formation of the benzyl cation, whereas the direct C-I cleavage channel yields the tolyl cations that rearrange to both benzyl and tropylium cations with dissimilar branching ratios among o-, m-, and p-isomers. With a two-photon energy of 3.87 eV at 640 nm, the direct C-I cleavage channel results in the product branching ratio, [tropylium cation]/[benzyl cation], in descending order, 0.16 for meta >0.09 for ortho >0.05 for para.