| Project/Area Number |
16K05682
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | National Institute of Advanced Industrial Science and Technology (2017-2018)
University of Tsukuba (2016) |
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Principal Investigator |
SEKIGUCHI AKIRA 国立研究開発法人産業技術総合研究所, 材料・化学領域, 招聘研究員 (90143164)
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| Project Period (FY) |
2016-04-01 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
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| Keywords | ケイ素－ケイ素三重結合化合物 / 高周期元素化学 / 多重結合 / 付加反応 / π電子化合物 / 有機ケイ素化合物 / 溶媒分離イオン対 / X線結晶構造解析 / ケイ素-ケイ素三重結合化合物 / 典型元素化学 / 有機ケイ素化学 / 構造有機化学 / 不飽和結合 |
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| Outline of Final Research Achievements |
The π bond formed between silicon atoms has a high energy level HOMO and a low energy level LUMO, resulting unusual chemical properties. Among them, disilyne 1 (R-Si≡Si-R, R = SiiPr[CH(SiMe3)2]2) has a trans-bent structure, different from a linear acetylene. Here, we investigated the reactivity of the disilyne 1 toward alkali metal halides and carbonyl compounds. The reaction of 1 with KF in THF underwent smoothly, producing a disilenide derivative with a solvent separated ion-pair, which was isolated by the addition of 2.2.2-cryptand. KCl, KBr, KI were also reacted with 1, giving the corresponding disilenides. The reaction with pseudohalides such as KSCN gave isothiocyanate disilenide. Reaction of the disilyne 1 with tetraphenylcyclopentadienone produced unexpected 4-oxa-2,3-disilabicyclo[3.3.0]octa-2,5,7-triene derivative with an oxygen-substituted 5-membered ring with a Si=Si bond. Unexpected product was also formed in the reaction of 1 with benzyl.
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| Academic Significance and Societal Importance of the Research Achievements |
従来は不安定で合成困難と考えられてきた種々の低配位及び多重結合高周期元素化合物について、立体保護のために独自に開発した置換基を用い、合成手法に関しても従来法にとらわれることのない自由な分子設計が可能な新しい方法論を提案、実践し、研究成果の有機元素化学における学術的意義は極めて高く、独創性も十分に高い。本研究から生み出された新規物質における新しい結合の概念や新規物質そのものが新材料開発などにも寄与するものと考えており、本研究は基礎研究としての典型元素化学及び応用指向の物質科学へと大きな波及効果を持つ先駆的な研究である。
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