| Project/Area Number |
10450340
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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 |
Synthetic chemistry
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| Research Institution | Yokohama National University |
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Principal Investigator |
ITO Takashi Yokohama National University, Faculty of Engineering, Professor, 工学部, 教授 (50016721)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAGUCHI Yoshitaka Yokohama National University, Faculty of Engineering, Research Associate, 工学部, 助手 (80313477)
MINATO Makoto Yokohama National University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (40239306)
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| Project Period (FY) |
1998 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥14,200,000 (Direct Cost: ¥14,200,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1999: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1998: ¥10,700,000 (Direct Cost: ¥10,700,000)
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| Keywords | group 6 transition metals / molybdenum / tungsten / bond-cleavage / bond-forming reaction / coordinative unsaturation / hydrido complexes / oxidative addition / モリブデンーケイ素結合 / フェニルシラン / ゲルマン / 5座配位子 / シクロペンタジエニル配位子 / モリブデン-ケイ素結合 / β-ジカルボニル化合物 / シクロペンタジェニル配位子 / 不斉還元 / 二酸化炭素 / C-H活性化 |
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| Research Abstract |
Transition metal polyhydrido complexes are known to be potent precursors of the coordinatively unsaturated species because they often release dihydrogen via reductive elimination on light irradiation or heating in solution. In view of the highly reactive nature of the coordinatively unsaturated intermediate thus generated toward oxidative addition reactions, the research program utilizing [MH_4 (Ph_2PCH_2CH_2PPh_2)_2](1, M=Mo, W) and [MH_2 (η^5-C_5H_5)_2](2, M=Mo, W) as starting complexes for the selective bond cleavage and bond formation was undertaken. Complex 1 affords coordinatively unsaturated intermediate {MoH_2 (Ph_2PCH_2CH_2PPh_2)_2} and/or {Mo (Ph_2P-CH_2CH_2PPh_2)_2} on irradiation or heating in solution by releasing one or two moles of dihydrogen. The reactive intermediates thus formed were found to react with (1) methacrylic esters to cause olefinic C-H bond activation, (2) allyl carboxylates to give an η^2-carboxylato complex and propene as a result of C-O bond activation, (3) β-diketones and catechols to give chelated diketonato and catecholato derivatives, respectively, (4) cyclic imines and amides to cleave their N-H bonds to give N-acylamido complexes, or finally (5) aryl silanes or germanes to give a novel hydrido-silyl or-germyl complex which has a quinquedentate ligand comprising of a P〜P〜Si/Ge〜P〜P framework. The last complex was further investigated in view of the reactivity resulting from its unique structure. Complex 2 gives, on protonation with the acid such as p-toluene sulfonic acid, cationic trihydirdo complex, which exhibits selective reduction of organic functional group such as carbonyl and imine. The system was found also to reduce allylic alcohols to propane. Finally synthesis of the hitherto unknown carbene derivatives of molybdenocene was attempted and some new complex of such type were obtained.
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