| Project/Area Number |
13440216
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Osaka University |
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Principal Investigator |
FUKUZUMU Shunichi Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (40144430)
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| Co-Investigator(Kenkyū-buntansha) |
SUENOBU Tomoyoshi Osaka University, Graduate School of Engineering, Assistant Professor, 大学院・工学研究科, 助手 (90271030)
OGO Seiji Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (60290904)
今堀 博 大阪大学, 大学院・工学研究科, 助教授 (90243261)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 2003: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2002: ¥4,500,000 (Direct Cost: ¥4,500,000)
Fiscal Year 2001: ¥5,100,000 (Direct Cost: ¥5,100,000)
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| Keywords | Oxidation / Electron Transfer / Multi-Nuclear Metal Complexes / Photocatalyst / Manganese Porphyrin / 地球環境 / エネルギー問題 / 電子移動 / 高原子価沖粗金属ポルフィリン |
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| Research Abstract |
Manganese(V)-oxo species are generated by the stepwise electron transfer oxidation of manganese porphyrins with two equivalents of tris(2,2'-bipyridine)ruthenium(III) (Ru(bpy)_3^<3+>) via formation of manganese(IV)-oxo species. Addition of Ru(bpy)_3^<3+> to an MeCN solution of olefins (styrene, cyclohexene) containing water in the presence of a catalytic amount of a series of several manganese porphyrins.affords epoxides, diols and aldehydes efficiently. Epoxides are converted to the corresponding diols by hydrolysis, and are further oxidized to the corresponding aldehydes which are four-electron oxidized products of olefins. Ethylbenzene is also oxidized to 1-methylbenzylalchol using (TMP)Mn^III(OH), (Cl_8TPP)Mn^III(OH) and (F_<20>TPP)Mn^III(OH), whereas adamantane is oxidized to 1-adamantanol only by using (Cl_8TPP)Mn(OH). The oxygen source in the substrate oxygenation was confirmed to be water using ^18O labeled water. The presence of H_2O is essential to accelerate the catalytic oxygenation of substrates with Ru(bpy)_3^<2+>. A manganese dendrimer promotes not only the catalytic two-electron oxidation of olefins but also four-electron oxidation to the corresponding aldehydes as compared with the monomer manganese porphyrin. The photocatalytic oxygenation of substrates with water has been made possible using cobalt(III) amine complexes, Ru(bpy)_3^<2+>, and water-soluble manganese porphyrins. The four-electron oxidation of water to oxygen has also been examined using multi-nuclear manganese porphyrins.
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