| Project/Area Number |
09102004
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| Research Category |
Grant-in-Aid for Specially Promoted Research
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| Allocation Type | Single-year Grants |
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| Review Section |
Chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
HIDAI Masanobu U of Tokyo.Dept.of Chem.& Biotech., Professor, 大学院・工学系研究科, 教授 (60011011)
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| Co-Investigator(Kenkyū-buntansha) |
NISHIBAYASHI Yoshiaki U of Tokyo, Dept.of Chem.& Biotech., Research Assistant, 大学院・工学系研究科, 助手 (40282579)
ISHII Youichi U of Tokyo, Dept.of Chem.& Biotech., Assoc.Professor, 大学院・工学系研究科, 助教授 (40193263)
MIZOBE Yasushi U of Tokyo, Institute of Industrial Sci., Assoc.Professor, 生産技術研究所, 助教授 (40175609)
SEINO Hidetake U of Tokyo, Institute of Industrial Sci., Research Assistant, 生産技術研究所, 助手 (50292751)
KUWATA Shigeki U of Tokyo, Dept.of Chem.& Biotech., Research Assistant, 大学院・工学系研究科, 助手 (10292781)
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| Project Period (FY) |
1997 – 1999
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥201,000,000 (Direct Cost: ¥201,000,000)
Fiscal Year 1999: ¥33,000,000 (Direct Cost: ¥33,000,000)
Fiscal Year 1998: ¥33,000,000 (Direct Cost: ¥33,000,000)
Fiscal Year 1997: ¥135,000,000 (Direct Cost: ¥135,000,000)
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| Keywords | dinitrogen complex / ammonia / molybdenum / tungsten / sulfur / polynuclear complex / chalcogenide cluster / catalytic reaction / ピロール |
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| Research Abstract |
The present study revealed that the cationic ruthenitum dihydrogen complexes trans-[RuCl (H_2)(diphosphine)_2]^+ derived from the coordinatively unsaturated ruthenium complexes and dihydrogen react with the tungsten dinitrogen complex cis-[W (N_2)_2 (PMe_2Ph)_4] to afford ammonia under mild conditions. This is the first esample of the transformation of coordinated dinitrogen into ammonia by using dihydrogen gas. Activation of dihydrogen gas on the sulfurbridged dimolybdenum complexes [(CpMo)_2S(SR)(S_2CH_2)]^+ and subsequent reactions with the tungsten dinitrogen complex also led to the formation of ammonia.
In connection with the structure of the active site of nitrogenase, general synthetic methods for homo-and heterometallic sulfur clusters ranging from trinuclear to pentanuclear clusters was established. A variety of homo-, heterobi-, and heterotrimetallic sulfido clusters containing group 4 -11 metals were systematically synthesized by these rational approaches. Furthermore, these polynuclear complexes were demonstrated to provide multimetallic centers effective for novel activation and transformation of reactivities of small molecules such as alkynes.alkenes. and isocyanides.
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