| Project/Area Number |
11166221
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas (A)
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
OSAKADA Kohtaro Research Laboratory of Resources Utilization, Prefessor, 資源化学研究所, 教授 (00152455)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥27,000,000 (Direct Cost: ¥27,000,000)
Fiscal Year 2001: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 2000: ¥19,500,000 (Direct Cost: ¥19,500,000)
Fiscal Year 1999: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Keywords | Organometallic Complex / Theoretical Chemistry / Transition Metal / Ligand Transfer Reaction / Multinuclear Complex / 分子軌道計算 / シリル配位子 / 金属間結合 / 白金 / ロジウム / 理論計算 / 有機遷移金属錯体 / トランスメタル化 / 複核錯体 / d軌道 |
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| Research Abstract |
The reactions of transition metal complexes having M-Si a-bond were investigated both from experimental and theoretical views. Pt(SiHPh_2)_2(Pme_3)_2 undergoes thermal elimination of diphenylsilane to produce a new trinuclear Pt complex, [Pt(ヲフ-SiPh_2)(Pme_3)]_3. The molecular orbital calculation revealed that it is the first example of trinuclear complexes composed of Pt(0) centers and electron-releasing ligands. The reaction of dimethyl acetylenedicarboxylate (DMAD) with [Pt(ヲフ-SiPh_2)(Pme_3)]_3 leads to transformation of the framework to linear triplatinum clusters. Sila-3-platinacyclobutene was isolated from the reaction of Pt(SiHPh_2)_2(Pme_3)_2 with DMAD and characterized by X-ray crystallography. The formation pathway was found to involve ヲテ-Si-H bond activation of the 3-sila-1-propenylplatinum intermediate that is formed by the insertion of a DMAD into a Pt-Si bond of Pt(SiHPh_2)_2(Pme_3)_2. The results provided a new mechanism for the general reaction of alkyne with organosilane catalyzed by Pt ; the cylcization pathway with a low energy intermediate is more plausible than the classic mechanism that involves silylenoid intermediate with an extremely high energy.
Rh and Ir complexes having halogeno (Cl, I) ligands and organosilyl ligands undergo coupling of these ligands to release the corresponding halosilanes. Dependence of the reaction rate on the structure of the complexes and on kind of the halogeno and silyl ligands revealed that the reaction involves intramolecular reductive elimination via concerted mechanism.
In summary, the present study involving experimenetal and theoretical approach has revealed various aspects of reactions of organotransition metal complexes and elucidated the mechanism of several synthetic organic reactions that involve transmetalation as a crucial step.
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