| Project/Area Number |
03640524
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | Kumamoto University |
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Principal Investigator |
SAKAKI Shigeyoshi Kumamoto University, Faculty of Engineering Professor, 工学部, 教授 (20094013)
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| Co-Investigator(Kenkyū-buntansha) |
ARAI Toru Kumamoto University, Faculty of Engineering Research Associate, 工学部, 助手 (50222716)
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| Project Period (FY) |
1991 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1992: ¥200,000 (Direct Cost: ¥200,000)
Fiscal Year 1991: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Keywords | Metalloporphyrin complex / Reduction catalysis / Hydrogenation catalysis / complex Iron gable porphyrin / cyclopropanation Catalytic / Iron porphyrin complex / 屋根型架橋ポルフィリン2核錯体 / ニトロベンゼン還元触媒反応 / α,β不飽和エステル却元触媒反応 / 亜硝酸還元酵素モデル反応 |
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| Research Abstract |
Reduction of nitrobenzene was performed by (TPP) FeCl and gable Fe_2Cl_2 as a model reaction of NO_2^- reduction by nitrite reductase. This reaction proceeds via not azobenzene and hydrazobenzene but nitrosobenzene and phenylhydroxylamine. Significant solvent effects were observed; reaction proceeds little in THF, moderately in diglyme, but considerably in diglyme-MeOH. The catalytic activity of gable Fe_2Cl_2 is about twice of (TPP) FeCl in diglyme-MeOH(1:1), suggesting that the two active cites in gable Fe_2Cl_2 cooperatively accelerates this catalytic reduction. UV-Vis and ESR spectra suggest that active species is Fe(II) porphyrin. Hydrogenation of alpha,beta-unsaturated esters and cyclopropanation of stylene were also efficiently catalyzed by these Fe-porphyrins, yielding the saturated ester and phenylcyclopropane respectively. In these reactions, however, gable Fe_2Cl_2 exhibits almost the same catalytic activity as (TPP)FeCl.
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