• Bulletin of the Korean Chemical Society
• /
• 제14권5호
• /
• pp.549-554
• /
• 1993

The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.

• Progress in Superconductivity
• /
• 제14권2호
• /
• pp.110-115
• /
• 2012

Samples with nominal compositions of $RuSr_2(Eu_{1.34-x}Tb_xCe_{0.66})Cu_2O_z$ (x = 0, 0.67) were prepared and their superconductivity and magnetic properties were compared to shed light on the effect of Tb substitution for Eu. X-ray diffraction measurements indicate that the Tb substitution resulted in a decrease in both a and c lattice parameters in consistent with ionic size difference between Eu and Tb. Contrary to the Tb-free sample, no superconducting transition behavior is observed in the Tb-sustituted sample. It is also found that the Tb substitution for Eu significantly increases the weak-ferromagnetic component of the field-cooled magnetic susceptibility as well as an increase in the magnetic ordering temperature. These results suggest that the magnetic state of the Ru sublattice is significantly affected by the Tb substitution for Eu.

• 한국세라믹학회지
• /
• 제23권2호
• /
• pp.43-49
• /
• 1986

By simple substitution of divalent cobalt nickel copper ion in the calcium-fluorapatite the ability to produce color was explored. To determine the solubility limit of cobalt nickel copper in the calcium-fluorapatite and the absorption spectrum with the addition of each transition elements XRD and visible range Spectroscopy were emp-loyed.

• 대한전기학회:학술대회논문집
• /
• 대한전기학회 1995년도 하계학술대회 논문집 C
• /
• pp.1242-1244
• /
• 1995

The dielectric and polarizable properties of $0.9Pb_{1-x}La_x({Mg}_{1/3}Nb_{2/3})O_3-0.1PbTiO_3$ (x=0,1,2,3,4,5) have been investigated. The temperature-dependant electrostictive characteristics of 0.9PMN-0.1PT relaxor ferroelectric system were improved by enhencing the extent of the diffuse phase transition(DPT). This was achieved using PMN-PTceramics by the partial substitution of La at the Pb site. The curie temperature and the maximum dielectric permittivity decreased by substituting La and the electric field-related hysteresis phenomena decreased with increasing La substitution amount.

• Progress in Superconductivity
• /
• 제11권1호
• /
• pp.67-71
• /
• 2009

The effect of Cu substitution on the structural and superconducting properties of the $(Ru_{1-x}Cu_x)Sr_2(Eu_{1.34{\cdot}}Ce_{0.66})Cu_2O_z$ system with x = 0, 0.25 and 0.5 prepared under ambient pressure have been investigated. The X-ray diffraction patterns indicated that the Ru ions are replaced by the Cu ions. It is found that the Cu substitution for Ru significantly reduces the ferromagnetic component of field-cooled magnetic susceptibility, but results in a small change in diamagnetic onset transition temperature of zero-field-cooled magnetic susceptibility. In contrast to the Ru $Sr_2(Eu_{1.34{\cdot}}Ce_{0.66})Cu_2O_z$, bulk Meissner effect is observed in the field-cooled magnetization measurements of the Cu doped samples. The experimental results are discussed in connection with the spontaneous vortex phase interpretation.

• Progress in Superconductivity
• /
• 제6권1호
• /
• pp.37-40
• /
• 2004

We investigated the effects of impurity doping on the electrical transport and magnetic properties of TEX>$(Ru, Sn)(Sr, La)<_2$$EuCeCu_2$$O_{z}$ samples. We found that Sn substitution fur Ru causes a significant decrease of the volume fraction of ferromagnetic phase, as well as a decrease of the temperature where the ferromagnetic component is observed. La substitution for Sr leads to an increase of the magnetic ordering temperature with a moderate change of ferromagnetic component. The experimental results are discussed in conjunction with the structural data, transport properties and a possible change of oxygen content.

• 대한화학회지
• /
• 제19권3호
• /
• pp.179-185
• /
• 1975

방향족 치환반응을 모형과하여 유사분자 착물이 천이상태가 될수있음을 단수 Huckel법으로 증명하고 새로운 방향족 치환반응의 기구를 제안하였다. 아울러 이 유사분자 착물을 양자역학적 선동법을 이용하여 안정화 에너지식을 유도하고 많은 탄소화합물의 안정화 에너지식을 유도하고 많은 탄소화합물의 안정화 에너지를 구하였다. 이 안정화 에너지로 어떤 방향족 화합물이 유사분자 착물을 형성하는 위치와 그 화합물의 치환반응의 결합 시약이 방향족 화합물에 부가반응이 일어나는 반응에까지 널리 설명할 수 있는 이점이 있다.

• Bulletin of the Korean Chemical Society
• /
• 제16권9호
• /
• pp.827-831
• /
• 1995

Kinetic studies on the reactions of five secondary acylic alkyl arenesulfonates with anilines are carried out in acetonitrile at 65.0 ℃. The magnitude of ρXZ determined (ρXZ=0.12-0.13) is slightly greater than that for the alicyclic series (ρXZ=0.11) under the same experimental condition. Ab initio MO results are found to support the slightly tighter transition state expected from the greater magnitude of ρXZ for the acyclic series. Despite the small variations, the magnitude of ρXZ and the theoretical transition state tightness remain relatively constant for the secondary carbon centers. Secondary kinetic isotope effects involving deuterated aniline nucleophiles show a successively smaller kH/kD(<1.0) value for a more sterically crowded reaction center carbon. This is in accord with the later transition state for bond-making predicted by the Bell-Evans-Polanyi principle for the more endothermic nucleophilic substitution reaction. Further support is provided by the results of the AM1 MO calculations on the reactions of secondary alkyl benzenesulfonates with chloride nucleophile.

• 한국세라믹학회지
• /
• 제34권2호
• /
• pp.139-144
• /
• 1997

결정학적으로 T' 구조인 Nd2-xCexCuO4-$\delta$ 회토류 구리산화물 초전도체는 지금까지 매우 복잡한 미세구조를 지닌 것으로써 잘 알려져 있다. 이 구리산화물 초전도체가 초전도 특성을 띠려면, Nd3+ 이온이 Ce4+ 이온에 의해 소량 치환되고 동시에 산소환원이 필요하다. 본 연구에서는 투과전자현미경의 수렴성 전자회절(CBED)패턴을 이용하여 Nd2-xCexCuO4-$\delta$ 의 Ce 미량 첨가와 미량의 산소환원에 따른 결정구조의 전이 발생 여부에 관하여 고찰하였다. 세 가지의 서로 다른 시편 Nd2CuO3,Nd1.85Ce0.15CuO4 와Nd1.85Ce0.15CuO3.965을 고상소결에 의하여 만들어 이들 각각 시편에 대한 CBED패턴을 주사투과전자현미경(STEM)으로 관찰하였다. 그리고 실험에 의하여 얻은 이들 HOLZ선들과 컴퓨터 계산에 의해 그려진 이론적인 HOLZ선들과 비교하는 방법에 의하여 Nd1.85Ce0.15CuO4의 격자상수를 구하였다.

• 대한화학회지
• /
• 제29권1호
• /
• pp.15-22
• /
• 1985

25$^{\circ}C$ 아세톤속에서 벤조일화합물과 피리딘류와의 친핵성치환반응을 속도론적으로 연구하였다. 전이상태 파라미터 $_{\rho}_S$, $_{\rho}_N$, ${\beta}$값으로 보아 생성물을 닮은 전이상태를 갖는 synchronous S$_N$2 반응메카니즘을 예상할 수 있었다. Potential Energy Surface 모형으로서 S$_N$2 반응메카니즘의 규명은 가능했으나 결합형성이 많이 진전되고 결합의 파괴는 약간 진전된 생성물에 더 가까운 전이상태 변화의 예측과 이탈능력 증가(Cl- ＜ CN-)에 따르는 전이상태 변화의 예측은 불가능하였다. Quantum mechanical 모형의 적용으로 이들 반응의 전이상태 역시 생성물을 닮은 구조임을 알 수 있었고 CN-이 Cl-보다 이탈능력이 좋음을 예측할 수 있었다.