1991 Fiscal Year Final Research Report Summary
Approach to Trivalent Silicenium Ion in Solution
| Project/Area Number |
02804036
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Tohoku University |
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Principal Investigator |
TERUI Yoriko Tohoku Univ., Organosilicon Research Lab., Instructor, 理学部, 助手 (00197815)
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| Co-Investigator(Kenkyū-buntansha) |
SEKEGUCHI Akira Tohoku Univ., Organosilicon Research Lab., Associate Professor, 理学部, 助教授 (90143164)
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| Project Period (FY) |
1990 – 1991
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| Keywords | Organosilicon Compound / Silicenim Ion / Disilene / Polysilane / Electron Transfer / Low-coordination / Radical Cation |
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| Research Abstract |
1. Attempts to prepare trivalent silicenium ion in solution were studied by the electron transfer reactions of disilenes such as tetramesitydisilene and tetrakis(bistrimethylsilylmethyl)disilene. However, no evidence for the intersediacy of the silicenium ion was obtained. 7, 7, 8, 8-Tetragethy-7, 8-disilabicyclo[2.2.2]octa-2, 5-diene, a new disilene precursor masked by benzene, was prepared by the high-pressure reaction.
2. DCA sensitized photoreactions of polysilanylalkanols afforded the cyclic silyl ethers arising from either intramolecular trapping of polysilane radical cations or silicenium ion intermediate. The reaction correlates well with sigma ^+ constants. The cyclic silyl ethers are also obtained on treatment with tris(P-brosophenyl)aainium salt.
3. Any appreciable regio-selectivity in the Si-Si bond cleavage can not be seen in DCA sensitized photoreaction of the linear polysilanes. However, the terminal Si-Si bond is cleaved predominantly with tris(P-brosophenyl)aminium salt.
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