• Bulletin of the Korean Chemical Society
• /
• v.18 no.10
• /
• pp.1050-1052
• /
• 1997

The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

• Bulletin of the Korean Chemical Society
• /
• v.12 no.4
• /
• pp.371-373
• /
• 1991

The crystal structure of eprazinone dihydrochloride, $C_{24}H_{32}N_2O_2$${\cdot}$2HCl, has been determined from 2102 independent reflections collected on an automated Nonious CAD-4 diffractometer using graphite-monochromated $Mo-K\alpha$ radiation. The crystals are monoclinic, space group P$2_1$/n, with unit cell dimensions a=11.381(2), b=28.318(2), c=7.840(1) $\AA$, $\beta=92.45(2)^{\circ}$, ${\mu}=2.37$ c$m^{-1}$, F(000)=968, and Z=4. Final R value is 0.071 for independent 2102 observed reflections. The molecule assumes an extended conformation. The piperazine ring has a normal chair conformation and the four carbon atom are planar with a maximum displacement of 0.004 $\AA$ for C(18) atom. The two chloride ions are hydrogen bonded to the two piperazine nitrogen atoms [N(14)${\cdot}{\cdot}{\cdot}$Cl(1); 2.986(6) $\AA$ N(17)…Cl(2); 3.084(8) $\AA$].

• Bulletin of the Korean Chemical Society
• /
• v.19 no.5
• /
• pp.527-530
• /
• 1998

This paper presents the electrochemistry and molecular orbital (MO) picture of a series of conformationally-restricted thioxantone derivatives. A series of $C_2-substituted$ thioxanthones were examined to probe the electronic influence of the substituent on the electrooxidation and electroreduction sites (i.e., on the electron densities at the 10-and 9-positions), respectively. In the presence of "electrophoric" groups such as C=O and S, characteristic electrochemical reduction and oxidation responses are observed. The electrochemical reaction was diffusion-controlled, because the $I_p/{\upsilon}^{1/2}$ ratio was constant for the anodic and cathodic wave of thioxantone derivatives. These substituent effects are presented in terms of correlations of oxidation (or reduction) potentials with the highest occupied molecular orbital (HOMO), or lowest unoccupied molecular orbital (LUMO) energies, respectively. There is good correlation between energies of the HOMO vs. $E_{pa}^{(+)}$ and energies of the LUMO vs. $E_{pc}^{(-)}$. Frontier Molecular Orbital (FMO) is changed by the functional group of thioxanthones. FMO energy level was offered us the information about the electron transfer direction, and the coefficient of FMO was offered the information about the electron transfer position. Sulfur atom has an important effect on oxidation potential, $E_{pa}^{(+)}$ and the carbonyl carbon has an important effect on reduction potential, $E_{pc}^{(-)}$. Therefore we were appreciated that the contribution of sulfur atom for the $E_{pa}^{(+)}$ and HOMO energies is larger than the contribution of carbonyl group for the $E_{pc}^{(-)}$ and LUMO energies.

• Nuclear Engineering and Technology
• /
• v.55 no.9
• /
• pp.3229-3240
• /
• 2023

Due to neutron radiation, atomic displacement has a significant effect on material in nuclear reactors. A range of secondary displacement models, including the Kinchin-Pease (K-P), Lindhard, Norgett-Robinson-Torrens (NRT), and athermal recombination-corrected displacement per atom (arc-dpa) have been suggested to calculate the number of displacement per atom (dpa). As neutron elastic interaction is the main cause of displacement damage, the focus of the current study is to calculate the atomic displacement caused by the neutron elastic interaction in order to estimate the exact amount of yield strength in a WWER-1000 reactor pressure vessel. To achieve this purpose, the reactor core is simulated by MCNPX code. In addition, a program is developed to calculate the elastic radiation damage induced by the incident neutron flux (RADIX) based on different models using Fortran programming language. Also, due to non-elastic interaction, the displacement damage is calculated by the HEATR module of the NJOY code. ASME E-693-01 standard, SPECTER, NJOY codes, and other pervious findings have been used to validate RADIX results. The results showed that the RADIX(arc-dpa)/HEATR outputs have appropriate accuracy. The relative error of the calculated dpa resulting from RADIX(arc-dpa)/HEATR is about 8% and 46% less than NJOY code, respectively in the ¼ and ¾ vessel wall.

• Journal of the Korean Chemical Society
• /
• v.21 no.3
• /
• pp.161-170
• /
• 1977

Several Pt(II) complexes containing glycine (or glycino anion) and styrene have been prepared, and their structures have been confirmed by infrared spectroscopy. The results confirm the structure of chloro(glycino)(styrene)platinum(II) in which the nitrogen atom of the chelated glycino anion is coordinated to the platinum in the trans position to styrene (N-trans isomer).

• Bulletin of the Korean Chemical Society
• /
• v.12 no.4
• /
• pp.438-440
• /
• 1991

Each aqueous solution (pH = 1) of acetic acid, acetamide, and acetonitrile produces carbon dioxide and hydrogen at 300 K when irradiated in the presence of semiconductors such as titanium dioxide, platinized titanium dioxide, etc. Similar results were obtained for each of benzoic acid, benzamide, and benzonitrile. Based on the relative amount of carbon dioxide, nitrile is believed to be transformed into carboxylic acid through the intermediacy of amide. A mechanism in which hydrogen atom and hydroxyl radical are involved is presented.

• Bulletin of the Korean Chemical Society
• /
• v.20 no.12
• /
• pp.1433-1436
• /
• 1999

The 2-(2,4-dimethoxyphenyl)-4-MDO (2) underwent polymerization with ring opening as well as cyclization reaction in the presence of various cationic catalysts such as boron trifluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid. They afforded a mixture of the ring-opened poly(keto ether) and 3(2H)-dihydrofuranone derivative. Both the methylene group and oxygen atom of 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The contents of the polymer and cyclization product were variable according to the acid strength of the cationic catalysts.

• Bulletin of the Korean Mathematical Society
• /
• v.58 no.2
• /
• pp.365-384
• /
• 2021

Let A be an expansive dilation on ℝn, and p(·) : ℝn → (0, ∞) be a variable exponent function satisfying the globally log-Hölder continuous condition. Let Hp(·)A (ℝn) be the variable anisotropic Hardy space defined via the non-tangential grand maximal function. In this paper, the author obtains the boundedness of anisotropic convolutional ��-type Calderón-Zygmund operators from Hp(·)A (ℝn) to Lp(·) (ℝn) or from Hp(·)A (ℝn) to itself. In addition, the author also obtains the duality between Hp(·)A (ℝn) and the anisotropic Campanato spaces with variable exponents.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.3
• /
• pp.306-310
• /
• 2003

Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

• Biomedical Science Letters
• /
• v.1 no.1
• /
• pp.89-94
• /
• 1995

Considering the planar structure and nonpolar properity of benzo(a)pyrene(B(a)p) and the planar heme part of cytochrome P-450, stacking interaction is probable. MO calculation on B(a)P and heme part of cytochrome P-450 were carried out to dertermine probable stacking interaction models. In this case, orbital interaction is most important. Accordingly, the stacking positions have high eigen vector in frontier orbital and boning type between two molecules. In this way, five probate models were selected and examined by MN2 and MO method. The most probable .stacking interaction model which is the 4, 5, 6 positions of B(a)P overlap carbon atom and pyrrole ring of ring of heme group was determined.