| Project/Area Number |
11450347
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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 | Nara Women's University (2000)
Osaka University (1999) |
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Principal Investigator |
OGAWA Akiya Nara Women's Univ., Fac.of Science, Professor, 理学部, 教授 (30183031)
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| Co-Investigator(Kenkyū-buntansha) |
HIRAO Toshikazu Osaka Univ., Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (90116088)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1999: ¥2,300,000 (Direct Cost: ¥2,300,000)
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| Keywords | Samarium Diiodide / Carbon-Fluorine Bond / Photoexcited Samarium Species / Reductive Coupling / Rare Earth Catalytic System / High Purity Synthesis of Polysilanes / Samarium Mixed System / Group 14 heteroatom Compounds / ポリシラン / 高純度合成法 / ケイ素-クロル結合 / 還元的縮合法 / レドックス反応系 / 低原子価希土類錯体 / フッ素化合物 / ケイ素-ハロゲン結合 |
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| Research Abstract |
It has been revealed that the irradiation with visible light enhances the reducing ability of samarium diiodide. While the reduction of organic fluorides with SmI_2 alone is difficult, irradiation with visible light causes the efficient reduction of organic fluorides to the corresponding hydrocarbons. Next we examined the application of this system to the reductive cleavage of Si-Cl bonds. After lots of effort, the reductive coupling of chlorosilanes is found to take place effectively by using samarium diiodide, samarium metal, and magnesium metal, giving the corresponding disilanes in good yields. Even in the absence of magnesium metal, the reductive dimerization of silyl chlorides proceeds to give the corresponding disilanes in relatively lower yields, whereas the presence of both samarium diiodide and samarium metal is essential. A catalytic amount of samarium diiodide is found to cause reductive coupling of organic tin chlorides and organic germyl chlorides with magnesium metal as a co-reductant efficiently even in the absence of samarium metal. The reduction system of chlorosilanes is successfully applied to the formation of polysilanes. Phenylmethyldichlorosilane is reductively polymerized to produce the polysilane with narrow and normal molecular weight distributon. The UV-visible spectra of polysilanes indicate the absorption based on the σ-conjugation of Si-Si at 340 nm, suggesthg the high purity of polysilanes synthesized by this samarium method. This finding indicates that this polymerization method is of potential for polysilnae synthesis.
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