| Project/Area Number |
06650954
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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 |
工業物理化学
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| Research Institution | Nagasaki University |
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Principal Investigator |
ONISHI Masayoshi Faculty of Engineering, Nagasaki University, Associate Professor, 工学部, 助教授 (00039695)
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| Project Period (FY) |
1994 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| Budget Amount *help |
¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1995: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1994: ¥1,200,000 (Direct Cost: ¥1,200,000)
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| Keywords | Liquid phase dehydrogenation / Hydridocobalt / Photocatalysis / Phosphonite / Cobalt / Energy strorage system |
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| Research Abstract |
The photochemistry of organometallic complexes has been one of the currently active research-fields, and much effort has been focused on the properties of photogenerated short-lived organometallic fragments with coordinative unsaturation and high catalytic activities. We have reported that photoirtadiation of tetrakis (diethylphenylphosphonite) hydridocobalt (I) [Co-HL_4] (L=PPH (OEt)_2) gives a transient hydridocobalt (I) species "CoHL_3" with dissociation of one coordinated phosphonite ligand L.Catalytic activities of the photogenerated CoHL_3 species have been realized in many homogeneous reactions, involving double-bond migration of olefins and hydrogen transfer from secondary alcohols to ketones. The present study deals with photoassisted dehydrogenation of 2-propanol in the liquid phase with the hydrido (phosphonite) cobalt (I).
The hydridocobalt (I) complex CoHL_4 under Pyrex-filtered photoirradiation catalyzed dehydrogenation reaction of 2-propanol in the liquid phase, with release of acetone. The turn-over number evaluated for the dehydrogenation for 1h at 82ﾟC was 4.6, and the quantum yields for the reaction at 366nm were determined to be about 0.015 at 60 and 82ﾟC.The dehydrogenation was characterized as a photoassisted-type catalytic reaction, and the photo generated hydrido transient CoHL_3 was attributed to a key-role-playing inter mediate in the catalytic cycle of the dehydrogenation.
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