• Bulletin of the Korean Chemical Society
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• 제16권1호
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• pp.30-33
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• 1995

UV photolysis of the titled polysilane (Me3Si)3SiMe (I) in the presence of a trapping agent of 2-propenol has been performed to investigate the interaction of short-lived silicon species formed from the photolysis of I with 2-propenol. Product studies show that the Me(Me3Si)Si: (II) and (Me3Si)3Si${\cdot}$(III) are primarily formed as the major reactive species which saturate their valencies via O-H insertion and H-abstraction, respectively. Some products are unstable toward further secondary reaction such as photodissociation and intermolecular reaction. The PM3 semiempirical calculations are performed to deduce the energetics of the photoinduced chemical reactions of I with the substrate.

• Bulletin of the Korean Chemical Society
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• 제3권2호
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• pp.37-44
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• 1982

In this work we have studied the multilayer stepwise adsorption of gases on solid adsorbents based on the previously developed theory. It is shown that stepwise adsorption isotherms emerge from our theory if an ad hoc adsorption regarding the degree of occupation for each successive layer is abolished and the effect of lateral intermolecular interactions among adsorbate molecules is included. In addition to these the effect of vertical interactions has also been taken into consideration. It seems that the vertical interaction plays a role in deciding the shape and the position of steps in resulting isotherms. It is evident from this research that it is the lateral interaction that is responsible for stepwise adsorption as long as the adsorbent surface is uniform and temperature is sufficiently low.

• Bulletin of the Korean Chemical Society
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• 제3권2호
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• pp.60-66
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• 1982

In relation to denaturation of proteins, thermally induced conformational change of poly(D-glutamic acid) was studied in the presence of poly(vinyl alcohol) at low pH, where poly(D-glutamic acid) undergoes a helix-to-${\beta}$ transition without any other polymer. In a dilute solution, poly(vinyl alcohol) enhanced the ${\alpah}-to-{\beta}_1$ transition of poly(D-glutamic acid) due to intermolecular interaction between the two polymers. On the other hand, this conformational change was interrupted to a large extent in a concentrated solution, due to the interpenetration of poly(vinyl alcohol) chain into poly(D-glutamic acid) chain which prevented the intramolecular association of poly(D-glutamic acid) chain. A conformational change from ${\beta}_1\;to\;{\beta}_2$ of poly(D-glutamic acid) was observed for the films obtained by casting during annealing the mixture solutions. The ${\beta}_2$ content in the cast film increased with increasing poly(vinyl alcohol) content in the mixture.

• Bulletin of the Korean Chemical Society
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• 제1권3호
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• pp.83-87
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• 1980

The Murrell-Fueno type of the intermolecular perturbation approach was applied to the acid-catalyzed hydrolysis of diformamide. The results show that: (1) the attack of a water molecule on the protonated carbonyl carbon is favored over that on the unprotonated carbonyl carbon; (2) the ${\sigma}$-approach model of water is preferred to the ${\pi}$-approach model; (3) the major contributing term to the total energy is the Coulomb energy, $E_q$, especially in the ${\sigma}$-approach, while the contribution of $E_{ct}$ (and $E_k$) increases moderately in the ${\pi}$-approach; (4) the reaction is a charge-controlled one, a hard-hard type in the language of the HSAB principle.

• Bulletin of the Korean Chemical Society
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• 제3권3호
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• pp.110-115
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• 1982

Thermochemistry and photochemistry of picolyl chlorides were studied. The thermal reaction of 2-picolyl chloride in benzene afforded intermolecular condensation product. In the case of 3-picolyl chloride, this type of the reaction did not occur, but polymers were obtained. A cyclic hexamer, suggested by a molecular model, was not formed because of the steric strain and low reactivity. The thermal reaction of 4-picolyl chloride gave a cyclic hexamer as well as a polymer. The cyclic hexamer, identified by NMR spectrum, showed ${\lambda}_{max}$ at 460 nm. The cyclic hexamer was cloven to the linear structure. Photolysis of 2-picolyl chloride at 253.7 nm gave a para-isomer followed by polymerization. When a methyl hydrogen of 2-methylpyridine is substituted by $CH_3O$, iso-PrO, and EtO group, the photoisomerization to the corresponding anilines or para-substituted pyridines did not occur within the range of the time used for 2-picolyl chloride. Thermolysis of picolyl chlorides in an acidic methanol solution did not afford any product.

• Bulletin of the Korean Chemical Society
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• 제1권3호
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• pp.109-112
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• 1980

Ultraviolet spectrophotometric investigations were carried out on monoalkylbenzene-iodine systems in carbon tetrachloride. The results reveal the formation of one-to-one molecular complexes. On the basis of the equilibrium constants for these complexes of representative monosubstituted benzenes, the following order of increasing stability is obtained: i-propyl- ${\Delta}$H, ${\Delta}$G and ${\Delta}$S for the interaction of a number of monoalkyl substituted benzenes with iodine have been determined. In general, it can be said that as ${\Delta}$H becomes increasingly negative, corresponding decreases in the ${\Delta}$G and the ${\Delta}$S values are observed, and these variations are linear. The thermodynamic constants become increasingly negative with increasing monoalkyl substitution of the aromatic donor nucleus. The complex bond is therefore weak, and its formation is accompanied by relatively small entropy changes. Thus, analysis of these findings is discussed.

• Bulletin of the Korean Chemical Society
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• 제10권2호
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• pp.138-142
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• 1989

Three oxovanadium(IV) complexes with bidentate ligands having only oxygen donor atoms, benzohydroxamic acid (Hben), 8-hydroxyquinoline-N-oxide(Hhqno) and picolinic acid-N-oxide (Hpicn) are prepared and magnetic and spectroscopic properties are investigated for the complexes $VO(ben)_2,\;VO(hqno)_2\;and \;VO(picn)_2.$ Magnetic data together with IR results strongly indicate that dimeric intermolecular interaction is significant in $VO(ben)_2$ while the presence of polymeric V-O${\cdot}{\cdot}$V-O interaction is suggestive in $VO(picn)_2$. For all three complexes, three electronic d-d transitions were observed; extremely strong optical absorption of these bands of $VO(ben)_2$ in DMSO are supposed to be arised from a great metal-ligand covalency. Some fundamental vibration modes of oxovanadium(IV) complexes were empirically assigned from the differences in the spectrum of metal complexes with free ligand.

• Bulletin of the Korean Chemical Society
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• 제21권8호
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• pp.793-796
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• 2000

In the neat flow vacuum pyrolysis of 2-methoxy-2-(o-N,N+dimethylaminomethyl)phenyl-3-trimethylsilyl-5,5-dime-thyl-2-silahexane (4) at $600^{\circ}C$ and its static thermolysis at $350^{\circ}C23-benzo-5-aza-1-silacyclohexane$, (5) has been obtained in97% and 46％ y ields, respectively. Product 5 might have been formed via an intramolecular rearrangement invoIving a zwitterionic species generated from the pentacoordinated silene Si-atom. From trapping experiments with an excess of MeOH, we have obtained 2-(o-N,N-dimethylaminomethyl)phenyl-5,5-dimethyl-2-trimethylsiloxy-2-silahexane (6) and 2-(o-N,N-dimethylaminomethyl)phenyl-2-methoxy-5,5-dime-thyl-2-silahexane (7) formed via an intermolecular protodesilylation reaction rather than through trapped prod-ucts of the silene.

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.427-430
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• 1999

The Grignard coupling reaction of bis(chloromethyl)diorganosilanes [(ClCH2)2SiR1R2: R1 = R2 = Me, la; R1 = Me, R2 = Ph, lb; R1 = R2 = Ph, lc] with diorganodichlorosilanes [(Cl2SiR3R4: R3 = R4 = Me, 2a; R3 = Me, R4 = Ph, 2b; R3 = R4 = Ph, 2c] at THE reflux temperature gave the intermolecular C-Si coupling product of 1,1,3,3-tetraorgano-1,3-disilacyclobutanes 3a-f in poor to moderate yields ranging from 7% to 50% along with polydiorganosilapropanes. The cyclization reaction of la-c with methyl-substituted dichlorosilanes 2a, b gave 1,3-disilacyclobutanes 3a-c, e, d in moderate yields (42-50%), while the same reaction with dichlorodiphenylsilane (2c) to 1,3-disilacyclobutanes 3d, f resulted in low yield (7-18%) probably due to the steric hindrance of two-phenyl groups on the silicon of 2c.

• Bulletin of the Korean Chemical Society
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• 제18권5호
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• pp.501-509
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• 1997

In recent papers[Bull. Kor. Chem. Soc. 1996, 17, 735; ibid 1997, 18, 478] we reported results of molecular dynamics (MD) simulations for the thermodynamic, structural, and dynamic properties of liquid normal alkanes, from n-butane to n-heptadecane, using three different models. Two of the three classes of models are collapsed atomic models while the third class is an atomistically detailed model. In the present paper we present results of MD simulations for the corresponding properties of liquid branched-chain alkanes using the same models. The thermodynamic property reflects that the intermolecular interactions become weaker as the shape of the molecule tends to approach that of a sphere and the surface area decreases with branching. Not like observed in the straight-chain alkanes, the structural properties of model Ⅲ from the site-site radial distribution function, the distribution functions of the average end-to-end distance and the root-mean-squared radii of gyration are not much different from those of models Ⅰ and Ⅱ. The branching effect on the self diffusion of liquid alkanes is well predicted from our MD simulation results but not on the viscosity and thermal conductivity.