| Project/Area Number |
13440185
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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 |
Organic chemistry
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| Research Institution | University of Tsukuba |
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Principal Investigator |
SEKIGUCHI Akira University of Tsukuba, Department of Chemistry, Professor, 化学系, 教授 (90143164)
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| Co-Investigator(Kenkyū-buntansha) |
ICHINOHE Masaaki University of Tsukuba, Department of Chemistry, Assistant Professor, 化学系, 講師 (90271858)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2003: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2001: ¥7,700,000 (Direct Cost: ¥7,700,000)
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| Keywords | Heavier Group 1-4 Element / Organosilicon Compound / Organogermanium Compound / Unsaturated Small Ring Compound / Radical Species of Heavier Group 14 Element / Cation Species of Heavier Group 14 Element / Anion Species of Heavier Group 14 Element / Multiple Bond Compounds of Heavier Group 14 Element / 高周期14族元素不飽和環状化合物 / シクロブタジエンジアニオン / シクロブタジエンコバルト錯体 / 有機スズ化合物 / 高周期14族元素不飽和小員環化合物 / 14族元素多重結合化合物 / シリルカチオン / シリルラジカル / シリルアニオン / ケイ素π電子系化合物 |
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| Research Abstract |
We have studied the reactivity of unsaturated small ring compound consisting of heavier Group 14 Elements such as silicon and germanium. The following results have been obtained in this project
(1)The Reaction of Cyclotrisilene : Synthesis and Structure of Cyclotetrasilenylium Ion
The reaction of ^tBu_2MeSi-substituted cyclotrisilene with [Et_3Si(C_6H_6)]^+・TPFPB^-in benzene gave cyclotetrasilenylium・TPFPB^-(TPFPB-=(C_6F_5)_4B^-) as air-and moisture-sensitive yellow crystals. X-ray crystallography revealed that the cyclotetrasilenylium ion is not only a free cation without the Interaction with counter anion and solvent molecules, but a 2π-electron homoaromatic compound consisting of silicon
(2)Reactivities of Cyclotetrasilenylium Ion : Synthesis and Structure of Cyclotetrasilenyl Radical and Cyclotetrasilenylide Ion
The reaction of the Cyclotetrasilenylium ion^-with bulky trialkylsilylsodium afforded cyclotetrasilenyl radical as a stable crystalline compound through the one electron reduct
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ion. The crystallographic analysis reveals that the cyclotetrasilenyl radical is a free silyl radical, having an allyl type delocalized structure, without any intermolecular interaction. Two electron reduction of the Cyclotetrasilenylium ion was also achieved by Li, Na, and KC_8 in diethyl ether to give cyclotetrasilenide ion. Stepwise chemical oxidation of cyclotetraslienid successfully regenerates the cyclotetrasilenyl radical and the Cyclotetrasilenylium Ion, indicating that cyclotetrasilenyl cation, radical, and anion show chemically reversible two electron redox system on the allyl type silicon π-electron system
(3)The Reaction of Disilagermirene with Divalent Species of Germanium and Tin
Disilagermirene derivatives with Si=Si or Si=Ge double bond react with dichlorogermylene-1,4 dioxane complex to give disiladigermetene, which have an endocyclic Ge=Ge double bond. The same type ring expansion took place in the reaction of disilagermirenes with dichlorostannylene-1,4 dioxane complex to afford unsaturated four membered ring compound bearing Ge=Sn double bond Less
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