Th.--Sci. phys.--Grenoble 1, 1977. N°: 20.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24625号 / 工博第5131号 / 新制||工||1981(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 松原 誠二郎, 教授 中尾 佳亮, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25297号 / 工博第5256号 / 新制||工||2000(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 松原 誠二郎, 教授 中尾 佳亮, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

>Magister Scientiae - MSc / In this thesis we describe the synthesis of several carbonyl complexes of molybdenum and tungsten, compounds (Cl-ClO). The compounds Cl- C4 are zero valent carbonyl complexes containing N-base ligands prepared by following a common synthetic procedure. Compounds Cl and C2 were metal pentacarbonyl of 3-(1-methylpyrrolidin-2-yl) pyridine while C3 and C4 are metal tetracarbonyl complexes of 3, 5- dimethylpyrazole, (M=Mo, W). The compounds C5-C10 are divalent metal carbonyl complexes. Compounds CS and C6 were 3,5-dimethylpyrazole dibromotricarbonyl metal complexes prepared from the dibromotetracarbonyl metal dimers at room temperature while the compounds C7 and C8 were cyclopentadienyl halogenoaryltricarbonyl complexes prepared from the cyclopentadienyl metal dimers. Compounds C9 and ClO were prepared from cyclopentadienyl metal dimers by reacting the [CpM(C0)3r anion with CCl4 to obtain [CpM(C0)3Cl] and further reacted with 3-(1- methylpyrrolidin-2-yl) pyridine. All the compounds, Cl-ClO, were characterized by the standard analytical techniques such as FTIR, 1H, 13C NMR; and UV-Vis spectroscopy. Compound C4 was characterized by X-ray crystallography. The structure is depicted as having a distorted octahedral geometry around the metal centre. The compounds Cl-ClO were then tested towards the epoxidation of selected cyclic and straight chain alkenes. The substrates used were cis-cyclooctene (Cyg), 1-octene (C8) cyclohexene (Cy6), 1-hexene (C6) and styrene (Sty). The epoxidation reactions were carried out at a temperature of 55 °C using tertbutylhydroperoxide (TBHP) as the oxidant and dichloroethane (DCE) as the solvent. The metal carbonyl complexes were pre-activated by first reacting them with the oxidant TBHP to obtain the metal-oxo complexes which are the active compounds for epoxidation reactions. The products were analyzed using GC techniques. The compounds, Cl-ClO showed a promising activity towards epoxidation reactions owing to the high conversions obtained by these compounds. For example, conversions of 81% (1-octene), 90% (cis-cyclooctene) were obtained by compound C5, 87% (cis-cyclooctene-compound C3, 95% (cis-cyclooctene-compound · C7) and 69% (ciscyclooctene- compound C4) for an average period of 24 h. The divalent metal carbonyl complexes showed a higher activity but with poor selectivity towards the expected epoxides compared to the zero valent metal carbonyl complexes.

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