D¹및 d²전자구조를 갖는 전이원소 착물의 자기 모멘트에 대한 온도, 일그러짐 및 Orbital Reduction Factor의 영향

徐赫春 圓光大學校大學院 1982 學位論叢 Vol.8-2 No.-

General forrnulas to calculate the magnetic moments for d¹ and d² transition metal complexes have been derived and the effects of orbital reduction factor (k), distortion (δ) and temperature on the calculated magnetic moments are investigated. The calculated magnetic moments increase as the orbital reduction factor is increased, such effects of distortion and temperature on the calculated magnetic moments can be observed. The calculated magnetic moments for dl complex fall in the range of the experimental values but those for d¹ complex are slightly higher than those for the experimental values.

메탄올중 치환 2-Phenylethyl Benzenesulfonates와 1,4-Diazabicyclo[2.2.2]octane의 반응속도에 미치는 이탈기효과

한광래,서혁춘,이국행 全北大學校 科學敎育硏究所 1988 과학과 과학교육 논문지 Vol.13 No.-

Leaving group effects for the reaction of substituted 2-phenylethyl benzenesulfonates with 1,4-diazabicyclo[2.2.2]octane were studied conductometrically in methanol at 44.5℃ and 54.5℃ The rate constants were calculated by Guggenheim equation and activation ther-modynamic parameters were also evaluated. The rates of reaction were increased with electron donating ability of substituent in substrate and with electron withdrawing ability of substituent in leaving group. The isokinetic relationship between △H^≠vs.△S^≠ was well correlated and this reaction is entropy controlled. The Hammett plots were correlated with good linearity and the value ρz is 0.96. From the activation parameters and the Hammett relationship, this reaction was. found dissociative S_N2 mechanism.

Crown Ethers Thorium(Ⅳ) Nitrate Hydrate 착물에 관한 연구

정학진,서혁춘 조선대학교 기초과학연구소 1986 自然科學硏究 Vol.9 No.1

The hydrated thorium(Ⅳ) nitrate have been reacted with the crown ethers of the different cavity size in methanol and aceton solvent, respectively. The properties and structures of these complexes are discussed by the element analysis, Kahl-Fisher moisture titration, thermal analysis, X-ay diffraction, ultraviolet and infrared spectroscopy, and electric conductivity. All of the complexes and the nonaccordinated systems with the three, four and five molecules of the hydrates, and the mole ratio of metallic ion to crown ether ligands are 1:1. The structures of the all complexes are different in accordance with the kinds of solvents, but coordinating number and mole ratio are constant in all complexes. The molar absorptivity of the complex obtained in aceton solvent is increased by coordinated bonding of the thorium(Ⅳ) ion to the ligands because the coordinating power of molecule of aceton is larger than that of water. The hydrated thorium(Ⅳ) nitrate complexes with crown ethers have the structure of 1:4 electrolytes deduced from 466-479 ohm^-lcm M^-1. These complexes have been formed by the electrostatic attraction and it is found the hydrated thorium(Ⅳ) nitrate complex with 15-crown-5 ligand is the most stable because thorium(Ⅳ) ion is bonded inside of the ligands. Whereas the other complexes are bonded outside of the cavity of the crown ether because the size of thorium(Ⅳ) ion is smaller or larger than that of the other crown ethers.

VIBRATIONAL STRUCTURE OF THIOCARBONYL HALIDES,CSX_2(X=F,Cl,Br)

Lee, Han Hee,Soe, Huck Choon,Han, Gwang Rae,Lee, Kuk Haeng 全北大學校 科學敎育硏究所 1994 과학과 과학교육 논문지 Vol.19 No.-

내부 좌표를 이용하여 사원자 분자인 Thiocarbonyl halide의 분자상수를 얻었다. 이 값을 Wilson의 GF matrix법에 대입하여 CSF_2, CSCl_2 및 CSBr_2의 기본 진동수를 계산하였는데 실험값 오차 범위내에서 잘일치하였다. 분자는 C_2형임을 규정했고 몇 가지의 상수들은 할로겐 원소들의 규칙성을 보였다.

네자리 Schiff base ligand를 갖는 금속착물에 관한 연구(Ⅱ)

정오진,서혁춘,김호두 조선대학교 기초과학연구소 1986 自然科學硏究 Vol.9 No.1

The terradenate schiff base ligand, N-N’-bis(salicyliden) -1.8-naphthalenediamine, has been synthesized from salicylaldehyde and 1.8-naphthalenediamine by Duff reaction. This schiff base ligand has been reached with Pd(Ⅱ), Rh(Ⅲ) and Nb(Ⅴ) metallic ion to form new complexes : Pd(Ⅱ) C_24H_15N_2O_2·2H2O, Rh(Ⅲ) C_24H_15N_2O_2·2H2O and Nb(Ⅴ) Cl_2·C_24H_16N_2O_2·4H_2O. The compositions and structures of the ligand and complexes have been discussed by element analysis, Kahl-Fischer's moisture titration method, thermal analysis, ultraviolet speectroscopy, infrared spectroscopy, ^1H nmr spectroscopy, X-ray diffraction patterns and electric conductance, respectively. Ⅰ. is clear that the Pd(Ⅱ) and Rh(Ⅲ) complexes have the structure of the hexacoordinating, and Nb(Ⅴ) has octacoordinating system. The mole ratios of metallic ions to ligard for all of the complexes are 1:1 and all of the complexes with tetradenate schiff base ligand have been coordinated with one, two and four molecules of water in accordance with the kind of complexes. Only the Rh(Ⅲ) complex has the structure of the dimmer bridgbonded with oxygen atom. The Pd(Ⅱ), Rh(Ⅲ) complexes are nonpolar but Nb(Ⅴ) complex is polar molecule dissociated with the Nb(Ⅴ) (C_14H_12N_2O_2). 4H_2O^3+.3Cl^- and has structure Of 1:3 electrolytes. All of the complexes form the d-d and d-π^* charge transfer complex between ligand and metal.

디메틸술폭시드용매중에서 Thorium (IV)-Crown Ether 착물의 산화-환원 반응메카니즘

정학진,정오진,서혁춘,Jung, Hak-Jin,Jung, Oh-Jin,Suh, Hyouck-Choon 대한화학회 1987 대한화학회지 Vol.31 No.3

DMSO와 $H_2O$용매 중에서 결합구조가 밝혀진 동공의 크기를 달리한 토륨(IV) 착물들의 전기전도도를 측정하여 해리현상과 전해질의 행동을 알아 보고 DMSO용매중에서 polarography와 cyclic voltammography적 거동을 조사하여 합성착물의 산화환원반응 메카니즘, 가역성을 알아 보고 환원과정에 관여하는 전자수 및 착물의 확산계수를 계산하였다. 그 결과 반양성자성 용매에서 모든 착물들은 1:1전해질로, 물에서는 1:4전해질로 각각 행동하고, DMSO용매중에서 각 착물의 환원반응은 1전자 1단계의 환원반응으로 가역적이며 확산계수는 착물종에 따라 $5.831{\times}10^{-6}{\sim}6.900{\times}10^{-6}$이었다. 그리고 모든 착물의 물분자는 -1.8V(대조전극, SCE)이상에서 분해를 일으켜 수소기체를 발생한다. The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

세자리 Schiff base ligand 금속착물에 관한 연구(Ⅰ)

정학진,정오진,서혁춘 조선대학교 기초과학연구소 1986 自然科學硏究 Vol.9 No.1

The tridenate schiff base legand, 2-(salicyliden imino) -p- cresol, has been synthesized from salicylialdehyde and 2-amino- p- cresol by Duff method. This schiff base ligand has been reacted with Pd(Ⅱ), Rh(Ⅲ) and Nb(Ⅴ) metallic ions to form new complexes: Pd(Ⅱ)C_14H_12NO_2·H_2O, Rh(Ⅲ)C_14H_12NO_2·2H_2O and Nb(Ⅳ)(C_14H_12NO_2)_2·2H_2O Cl. The compositions and structures of the ligand and complexes have been discussed by element analysis, Kahl Fischer's moisture titration method, thermal analysis, ultraviolet spectroscopy, infrared spectroscopy, ^1H-nmr spectroscopy, X-ray diffraction patterns and electric conductance, respectively. It seems the Pd(Ⅲ) and Nb(Ⅴ) complexes have the structure of tetra- , hexa-and oct-acoording system, respectively and the mole ratio of metallic ion to ligand for the Pd(Ⅱ) and Rh(Ⅲ) complex are 1:1, but Nb(Ⅴ) complexis 1:2. Pd(Ⅱ), Rh(Ⅲ) and Nb(Ⅴ) complex with tridenate schiff base ligand have been coordinated with one and two molecules of water in accordance with the kinds of complexes, and the Rh(Ⅲ) complex has the structure of dimer bridge bonded with oxygen atom. The Pd(Ⅱ) and Rh(Ⅲ) complexes are nonpolar molecules but Nb(Ⅴ) complex is a polar molecule which will be dissociated in Nb(Ⅴ)(C_14H_12NO_2)_22H_2O.Cl^- and has structure of 1:1 electrolyte. All of the complexes have phenomena of π- π^* in ligand and d-d and d-π^* charge transfer between ligand and metal.

새로운 Thorium (IV)-Crown Ether 착물형성

정학진,정오진,서혁춘,Jung, Hak-Jin,Jung, Oh-Jin,Suh, Hyouck-Choon 대한화학회 1987 대한화학회지 Vol.31 No.3

A series of new thorium nitrate complexes with crown ethers have been synthesized from the reaction of the hydrated thorium nitrate, with the appropriate crown ethers of different cavity sizes in various solvents such as methanol, ethanol, butanol, methylacetate, acetone, tetrahydrofuran and acetylacetone. CHN elemental analysis, ICPAS, thermal analysis and Karl-Fischer method have been used to characterize their compositions, and the spectroscopic methods of IR, UV, $^1H-NMR$, and X-ray diffraction have been employed to determine the structures and solvolysis phenomena of these complexes. and the electrical conductances were measured in DMSO, and water solvent. The solvolysis have been observed only in the complexes synthesized in acetylacetone solvent. In the solvated complexes of 15-crown-5 and 18-crown-6, the mole ratio of $Th^{4+}$: ligand : acetylacetone is found to be 1:1:1, but in the non-solvated complexes of 12-crown-4 and 15-crown-5, the mole ratios of Th:L are 1:2 and 2:3, respectively, and that in the complexes of both 18-crown-6 and dicyclohexano-18-crown-6 is 1:1. All complexes which were not solvated have shown $n{\to}{\sigma}^{\ast}$ electronic transitions of crown ether whereas complexes solvated have exhibited both $n{\to}{\sigma}^{\ast}$ of crown ether and $n{\to}{\pi}^{\ast}$ transitions of acac. The dissociation mole ratio of $Th^{4+}$ and nitrate ion is found to be 1:1 in aprotic solvent, and 1:4 in protic solvent like water. 여러 용매(methanol, ethanol, butanol, ethylether, methylacetate, acetone, THF 및 acetylacetone)중에서 아직 보고된 바 없는 공동을 달리한 crown ether들을 리간드로 한 토륨(IV) 고체 착물을 합성하였다. 이 고체 착물에 대한 배위 화학적인 정보를 얻기 위하여 원소분석(C.H.N) 및 ICPAS법에 의한 토륨분상, 열분석과 Karl-Fischer적정법에 의한 착물중의 결정수 분석에 의해서 고체 착물들의 조성을 결정하였다. 그리고 적외선, 자외선 분광분석, $^1H$-핵자기 공명 분석 및 X-선 회절분석법에 의하여 각 합성 착물들의 결합구조에 대한 정보들을 얻었고 각 합성 착물들에 대한 용매화 현상을 논의하였다. 그 결과 아세틸아세톤 용매하에서 합성된 착물들은 아세틸아세톤을 제외한 모든 실험 용매중에서 합성된 crown ether를 가지는 토륨(IV) 착물들은 용매화 반응이 일어나지 않았다. $Th^{4+}$금속이온에 대한 리간드 결합비는 고리의 크기에 주로 영향을 받으며 12-crown-4의 경우는 1:1([$Th^{4+}$]:[lig.]) 착물, 15-crown-5의 경우는 2:3 착물 및 18-crown-6와 dicyclohexano-18-crown-6의 경우는 1:1 착물이었다. 용매화가 일어나는 15-crown-5 와 18-crown-6 착물의 경우는 1:1:1([$Th^{4+}$]:[lig.]:$[CH_3COCH_2COCH_3]$)이었다. 용매화하지 않는 모든 착물들은 crown-ether의 n-${\sigma}^{\ast}$전자전이를, 그리고 용매화된 착물은 crown-ether n-${\sigma}^{\ast}$와 acac의 $n-{\pi}^{\ast}$전자전이를 동시에 나타냈다. 반양성자성 용매에서 모든 착물들은 1:1전해질로, 물에서는 1:4전해질로 각각 행동하는 9배위자 착물임을 알 수 있다.

Computer Program에 의한 란탄계 선택성 막전극의 감응전위 측정

정학진,정오진,서혁춘,장동주 조선대학교 기초과학연구소 1985 自然科學硏究 Vol.8 No.1

Having made the selective membrane electrodes with lanthanide fluoride and lanthanide oxalate, the response potentials of 〔F^-〕 and 〔C_2O^2-_4〕 were measured with the selective membrane electrodes and the measured data were treated by using computer program. It was concluded that the analytical experiment done by the application of A/D converter to the personal computer reduced the analytical error and enhanced the reproductivity by means of the development project of computer program. The results were as follows: 1. When the additional ratio of matrixes is 0.1%, the response potentials of 0.1% matrixes were better than 0.3% in the response potentials. 2. The response values of the membrane electride mixed with silicon rubber as matrix is higher than those of the electrode mixed with PVC. 3. The response values of the membrane electrode with reference electrodes were better than that of membrane electrode with calomel electrodes and membrane electrodes. 4. Contrary to the calomel and membrane electrodes the denser concentration of the reference electrode, the less-the electric potential. 5. The response potentials of the insoluble membrane electrodes were inveresely proportional to the size of metallic ions. 6. The stability was the highest, as membrane eletrodes were in to the solution over 24 hours. 7. The response potential of La_2(C_2O_4)_3 and LaF_3 were stable between the range of pH 4.5∼8.0 and pH 3.5∼7.5 respectively.

有機溶媒中에서 Cr(II)과 p-Aminoazobenzene 및 그 誘導體와의 錯物에 關한 硏究

권오형,이국행,서혁춘 全北大學校 科學敎育硏究所 2001 과학과 과학교육 논문지 Vol.26 No.-

The study of the complexes between an acceptor molecule Cr(Ⅱ) and donor molecules, p-aminoazobenzene(AAB), N-methylarninoazobenzene (MAAB) and N.N-dimethylaminoazobenzene, was accomplished through UV-Vis spectrophotometric method. The complexes were formed in pure methanol, acetonitrile and mixed solvents of both, of which volume ratios were 3 : 1, 1 : 1, 1 : 3, respectively. Looking into absorption spectra of donors, as the polarity of solvent was increased, maximum absorption wavelength showed hypsochromic shift in AAB and MAAB, and bathochromic shift in DMAB. This is because the donor molecules in AAB and MAAB at the ground state are more polar than that at the excited state, while the donor molecules in DMAB at the existed state are more polar than that at the ground state. The complexes formed between green Cr(Ⅱ) and yellow donors showed red color, which are longer wavelength than acceptor and donors. As the solvent's polarity increased, absorption spectra of each complex showed bathochromic shift. This is because the effect of methyl group's electron donating effect increased the basicity of donors through interaction between methyl groups and p-aminoazobenzene. Therefore the basicity order between AAB and derivatives is AAB < MAAB < DMAB. The stability constants(K) and molar extinction coefficient (ε max) of each complex were calculated by using Benesi-Hildebrand method. This method and mole ratio results and the values of showed 103~105 L/mol·㎝ were considered to be 1:1 or 1:2 ratio complex. As the H atoms of NH2 are substituted by CH3, the stability constants increased. Regarding the donors' electron donating effect, the complex resulted from reactions between Cr(Ⅱ) and donors is considered ligand-to-metal charge transfer complex.