Grant-in-Aid for Specially Promoted Research
|Research Institution||Tokyo Institute of Technology|
MORO-OKA Yoshihiko Research Laboratory of Resources Utilization, Tokyo Institute of Technology, professor, 資源化学研究所, 教授 (70016731)
HIKICHI Shiro Research Laboratory of Resources Utilization, Tokyo Institute of Technology, assistant professor, 資源化学研究所, 助手 (10282857)
FUJISAWA Kiyoshi Research Laboratory of Resources Utilization, Tokyo Institute of Technology, assistant professor, 資源化学研究所, 助手 (10251670)
AKIRA Munetaka Research Laboratory of Resources Utilization, Tokyo Institute of Technology, associate professor, 資源化学研究所, 助教授 (50167839)
|Project Fiscal Year
1996 – 1998
Completed(Fiscal Year 1998)
|Budget Amount *help
¥165,000,000 (Direct Cost : ¥165,000,000)
Fiscal Year 1998 : ¥24,000,000 (Direct Cost : ¥24,000,000)
Fiscal Year 1997 : ¥31,000,000 (Direct Cost : ¥31,000,000)
Fiscal Year 1996 : ¥110,000,000 (Direct Cost : ¥110,000,000)
|Keywords||oxygen / transition metal complexes / dioxygen complex / metalloprotein / hydrotrispyrazolylborate / oxo species / poly(phenylene oxide) / 酸素 / 遷移金属錯体 / 酸素錯体 / 金属タンパク質 / ヒドロトリス(ピラゾリル)ボレート / オキソ種 / ポリ(フェニレンンオキシド) / ヒドロペルオキソ種|
In order to clarify functions and structure of the active sites of oxygenation catalysts and metalloproteins relevant to oxygen transport and oxygenation reactions, systematic synthetic study of transition metal-dioxygen complexes with hydrotrispyrazolylborates, which can easily modify the coordination electronic and steric environment by appropriate substituents, has been carried out. Key findings are as follows
1. Chemistry of high valent bis(μ-oxo) species
Dinuclear μ-η2:η2-dioxygen complexes of nickel and cobalt are converted via O-O cleavage to high valent bis(μ-oxo) species, which are capable of oxygenation of hydrocarbons. The compounds attract much attention due to their relevance to the active species of methane monooxygenase.
2. Oxygen activation on a mononuclear species
The function of metalloproteins containing mononuclear active center such as catechol dioxygenase, which oxidizes aromatics, has been successfully reproduced.
3. Synthesis of dioxygen complexes of second row metals and early transition metals
The target of the synthetic study has been extended to metals which are not involved in metalloproteins, and such study reveals the characteristic aspects of first row metal species found in the proteins.
4. Regioselective oxidative polymerization of phenols
The dicopper-dioxygen complexes prepared by us are found to be active for oxidative polymerization of phenols to give poly(p-phenylene oxide) in a regioselective manner. The result of a bioinorganic study has been applied to an industrial process.
Other aspects such as mononuclear copper-oxygen complexes relevant to copper enzymes and oxidation of aromatics in the absence of dioxygen are also studied.