| Project/Area Number |
59470036
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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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 | Osaka City University |
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Principal Investigator |
NAKAMURA Yukio Department of Chemistry, Faculty of Science, Osaka City University, 理学部, 助教授 (20047012)
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| Co-Investigator(Kenkyū-buntansha) |
ISOBE Kiyoshi Department of Chemistry, Faculty of Science, Osaka City University, 理学部, 講師 (70101285)
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| Project Period (FY) |
1984 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1986: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1985: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1984: ¥5,100,000 (Direct Cost: ¥5,100,000)
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| Keywords | Metal-Metal Bonds / Diphosphine Complexes / Model-Enzyme / Photochemical Reaction / Heterobinuclear Complexes / <mu> -Xylylene Complexes / μ-メチレン錯体 |
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| Research Abstract |
1. Reactions of M <(acac)_2> (M=Pd,Pt) with dppm(= <Ph_2> <PCH_2> <PPh_2> ) to from M <(dppm-H)_2> (dppm-H=a deprotonated dppm anion) and methylation of the carbanions in Pt <(dppm-H)_2> with MeI have been studied, and both the reaction schemes were elucidated with the aim of <^1H> , <^(13)C> , or <^(31)P> NMR spectroscopy.
2. Reactions of <[Pd(dppm)_2]^(2+)> with <[CpMo(CO)_3]^-> as a nucleophile was examined to obtain a certain heterobimetallic complex and the desired complex [ <(CO)_3> Mo <((mu)-dppm)_2> -PdCp] ( <PF_6> ) was synthesized and characterized. 3. Photochemical reactions of <[CpMo(CO)_3]_2> with <NO(_2^-)> or dark reactions of <[CpMo(CO)_2]_2> with <NO(_2^-)> and <NO(_3^-)> have been elucidated to give the mononuclear complex [CpMo <(CO)_2> (NO)], and the reaction mechanism was also proposed.
4. The nucleophilic attak of <[CpMo(CO)_3^-> at the benzyl carbons of <alpha> , <alpha> ' -dibromo-o, m, p-xylene was found to afford <mu> -xylylene complexes which react with <PMe_2> Ph to give acyl complexes. It was revealed that photo-irradiation of the <mu> -xylylene complexes induce homolytic cleavage of the Mo-C bond.
5. The redox behavior of <[Rh(C_5Me_5)Me]_2> <(mu)-CH_2)_2> were examined by cyclic voltammetry and the presence of three oxidation waves were recognized. A possible scheme on the oxidation was proposed based on the following experimental data: controlled potential electrolysis, analysis of the evolved gases, and ESR measurement of the electrolyzed solution.
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