| Project/Area Number |
14078206
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | The University of Tokyo |
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Principal Investigator |
MIZOBE Yasushi The University of Tokyo, Institute of Industrial Science, Professor, 生産技術研究所, 教授 (40175609)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥24,800,000 (Direct Cost: ¥24,800,000)
Fiscal Year 2005: ¥6,400,000 (Direct Cost: ¥6,400,000)
Fiscal Year 2004: ¥6,400,000 (Direct Cost: ¥6,400,000)
Fiscal Year 2003: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥6,000,000 (Direct Cost: ¥6,000,000)
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| Keywords | Metal cluster / Sulfido cluster / Selenido cluster / Thiolato complex / Metalloenzyme model / Mixed-metal polynuclear complex / Nitrogen fixation / Supramolecule synthesis / 金属カルコゲニド / 小分子の活性化 / 酸化反応 / DFT計算 / キュバン型クラスター / 超分子 / アセチレン錯体 / イソニトリル錯体 / ヒドロスルフィド錯体 / 遷移金属スルフィドクラスター / 遷移金属セレニドクラスター / ヒドロセレニド錯体 / 不完全キュバン型クラスター / 窒素固定モデル反応 / 触媒的ヒドラジン還元反応 / 貴金属クラスター / X線構造解析 |
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| Research Abstract |
1. Novel hydrosulfido-and hydroselenido-bridged dinudear complexes of Ir, Rh, and Ru containing the M(μ-EB)_2M cores (E=S, Se) have been isolated, which have proved to serve as versatile precursors to synthesize a variety of chalcogenido bridged homo-and hetermetallic clusters through dimerizartion or by treatment with certain transition metal compounds as well as main group metal species. The nuclearities of the produced dusters vary from three to seven. Trinuclear sulfido-thiolato duster of Ir [(Cp^*Ir)_3(_<μ3>-S)(_<μ2>-SH)_3]Cl has also been prepared, which has been found to be converted to a series of cubane-type Ir_3MS_4 dusters by incorporating certain M fragments.
2. Sulfido-bridged dinudear complexes of Mo, W, and Re containing the MS(μ-S)_2MS cores have been converted to a variety of incomplete cubane-type and cubane-type mixed-metal sulfido dusters. It is to be noted that trimetallic cubanes are readily available from Re precursor by the stepwise addition of two different metal sources.
3. Mixed-metal cubane-type Mo_2M_2S_4 dusters with oxo ligand (M=Ir, Rh) have been prepared, which have been found to catalyze the N-N bond cleaving reaction of methylphenylhydrazine in the presence of a proton source and reducing agent. Hydrazido duster as an intermediate stage of this nitrogenase model reaction has also been isolated and fully characterized.
4. Sulfido-and thiolato-bridged In and Ir2Ru dusters have been prepared and their reactivities toward small molecules such as CO, isocyanide, and alkynes investigated. For the former Ir3 duster, its ability to catalyze highly stereoselective cydotrimerization of terminal alkyne has been demonstrated.
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