Stabilities of chelates of 7-nitroso-8-hydroxyquinoline-5-sulfonate have been determined for divalent transition metal ions, Mn(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) by means of the Calvin-Bjerrum technique. Comparison of these stability constants with those obtained for 8-hydroxyquinoline, and 8-hydroxyquinoline-5-sulfonate shows that the observed differences are essentially the results of the lower basicity of the sulfonated group and different metal-ligand bond. The divalent metal chelate stability sequence is not in agreement with the reported metal orders for other chelating agents. The stabilities were found to follow the order Mn(Ⅱ) < Fe(Ⅱ) ${\approx}$ Co(Ⅱ) > Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ).

The resonance parameter value between the saturated carbon and unsaturated carbon atom in cyclopentadiene has been evaluated. And then cyclopentadiene has been investigated on the correlations between it's electronic structures and reactivities by means of the extended Huckel method proposed by R. Hoffmann.

基底狀態의 Porphin 核과 Phthalocyanine 核의 電子狀態와 反應性을 理論的으로 考察하였다. 이때 各 ${\pi}$軌道의 energy量과 superdelocalizability 및 結合次數(bond order)는 單純分子軌道法에 依據해서 算出하였다. 이 두 化合物의 경우, 最高被占軌道와 最底空軌道 사이의 energy 差가 一般的인 다른 有機化合物보다 상당히 적었는데, 이것은 곧 이 두 化合物이 勵起되기 쉬운 狀態에 놓여 있음을 뜻한다. 또한 superdelocalizability와 結合次數로서 이 두 化合物의 各 原子位置에서의 親電子的, 親核的 및 radical 反應의 反應性과 結合强度를 各各 決定하였다.

A series of Molybdenum thiocyanate complex has been prepared as new compound: $MoO_2(CNS)_2Py$, $MoO(CNS)_4Py$, $MoO_2(CNS){\cdot}3Py$, $MoO(CNS)_3{\cdot}2NH_3{\cdot}MoO(CNS)_3{\cdot}2HCONH_2$, where Py = Pyridine. Properties and configuration of the complexes were studied by chemical and physical method.

몇가지 ortho-hydroxy monoazo 化合物들을 合成하여 이것들을 遷移元素로 金屬化시켰다. 三酸化크롬, 酢酸銅 및 酢酸코발드를 이 金屬錯鹽生成反應에 使用하였다. 이 硏究에서 다음과 같은 事實들을 알 수 있었다. (1) 이 金屬錯鹽生成反應에서의 溶媒는 다른 여러가지 有機溶媒보다는 물이 가장 좋고, (2) 金屬錯鹽生成反應 混合液의 가장 適當한 液性은 pH=4.5~5.5程度 이었으며, (3) 이들 monoazo 金屬錯鹽의 물에 대한 溶解性은 主로 그 錯鹽의 組成에 달렸으나 어느 程度는 分子內의 黃酸基의 存在에 의하여서도 影響을 받는다. 그리고 (4) 分子當 두개의 ortho-hydroxy基를 가진 金屬錯鹽이 더 强한 結合能을 가지고 있다.

여러 酸性溶媒 속에서 3,4-methylenedioxy-${\beta}$-nitrostyrene에 대한 n-butylmercaptan의 親核性 添加反應速度常數를 측정하여 넓은 pH범위에서 잘 맞는 反應速度式을 구하였다. 이 식에 의하면 pH3이하에서는 mercaptan분자가 첨가하며 pH6이상에서는 mercaptide ion이 첨가함을 알 수 있고 이 중간 pH범위에서 일어나는 복잡한 반응 메카니즘도 이 식에 의해 정량적으로 잘 설명할 수 있음을 알았다.

Fe-EDTA complex, which is easily formed when Fe salt and EDTA.2Na are mixed in the aqueous medium, is found to be a very effective catalyst in the dehydropolycondensation of aminophenols. In the dehydropolycondensation of aminophenols, the catalyst, Fe(Ⅲ)-EDTA complex (higher oxidation state) is reduced to less stable Fe(Ⅱ)-EDTA complex (lower oxidation state), and the latter is easily oxidized by air to the original higher oxidation state complex, therefore the catalytic action of Fe-EDTA complex is found to be recycled effectively. Under the catalytic action of the above mentioned complex, p-aminophenol is polymerized in the aqueous medium to form the oligomers of p-aminophenol, which the degree of polymerization to be 5 or more. The oligomers formed contain partly quinone nucleus as well as amino and hydroxyl groups. In this study, the effects of the solvents and characteristics of the oligomers are discussed. These types of polymerizations catalyzed by the metallic chelate compounds are considered to be very closely related to the reactions in the living matters.

In the oligomerization of p-aminophenol under the catalytic action of the metallic complexes, the effects of the ligands are studied. When the initial velocity of $O_2$ uptake at pH 8 using Fe(Ⅲ) as the central metal and N-hydroxylethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 1,2-cyclohexanediaminetetraacetic acid(CyDTA) as the ligands respectively are compared, the velocities are as the following order: HEDTA > EDTA > DTPA > CyDTA. Further when the effect of the ligands, nitrilotriacetic acid (NTA), HEDTA, EDTA, and DTPA, on the yields of oligomers are compared, the result shows as the following order: NTA > HEDTA > EDTA > DTPA. These are nearly reverse order of the stability constants of the complexes. In order to determine the composition of the mixed complexes at the initial step, the method of continuous variation is used, and it is found that the composition ratio of Fe-EDTA complex to monomer in the mixed complexes is one at pH 5-8 range. It is also found that at pH 9 or in the more alkaline range, side reactions occur to form water soluble dimer of quinone type and the catalytic action of the metallic complex markedly decreases on account of the hydrolysis of the central metal by the $OH^-$ ion.

In the oligomerization of p-aminophenol by the catalytic action of Fe-EDTA complex in the aqueous medium, the mixed complex intermediate, Fe-EDTA-M type, is considered to be formed, from which active radicals of the monomer are produced. In this system, polymerization is presumed to proceed as follows: Free radical formation ${\to}$ Coupling ${\to}$ Activation ${\to}$ Coupling, and so on. In this study, the form of the monomer and coordination state in the mixed complex, the catalytic action of Fe-EDTA the complex, the reaction mechanism, and the structure of the oligomers are discussed.