2018 Fiscal Year Final Research Report
Syntheses and Reactivities of Silanimine- and Phosphasilene-coordinated Electron-deficient Complexes
Project/Area Number |
15K05443
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Research Category |
Grant-in-Aid for Scientific Research (C)
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Allocation Type | Multi-year Fund |
Section | 一般 |
Research Field |
Inorganic chemistry
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Research Institution | Hirosaki University |
Principal Investigator |
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Co-Investigator(Kenkyū-buntansha) |
太田 俊 弘前大学, 理工学研究科, 助教 (20733132)
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Project Period (FY) |
2015-04-01 – 2019-03-31
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Keywords | シライミン錯体 / ホスファシレン錯体 / 電子欠損錯体 / 反応場構築 / ルイス酸 / カルベニウムイオン |
Outline of Final Research Achievements |
Reaction of an electron-deficient silanimine-coordinated titanium complex with ketones yielded the insertion products between the titanium-silicon bond. In the reaction with 1,3-dimethyl-2-imidazolidinone, the unusual cleavage of the carbon-oxygen double bond has been achieved. We also synthesized the silanimine-bridged diruthenium complex, which reacted with carbon monoxide and isocyanides to give the products. The reaction can be explained by assuming 1,2-H-shift of the bridging hydrogen atom to the nitrogen atom and the Si-H reductive elimination. These reactions are potentially applicable to the coupling between hydroamine and dihydrosilane. The iridium complexes possessing phosphasilene and silanethione moieties were synthesized and uniquely characterized by X-ray diffraction study. Theses complexes were highly reactive toward polarized small molecules.
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Free Research Field |
有機金属化学
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Academic Significance and Societal Importance of the Research Achievements |
これまで遷移金属錯体触媒の多くでは、一連の反応は金属中心で進行することが仮定され、分子設計がなされてきた。一方、元素戦略的な観点からいうと、希少な遷移金属に頼ることなく、クラーク数の大きい主要族元素を反応活性点として触媒を設計できれば、持続可能な社会構築に寄与できる。本研究成果は、ケイ素、窒素、リン、硫黄、炭素といった主要族元素を用いて、将来的に触媒へと展開可能な反応場の構築を行った点で、学術的および社会的な意義は大きいといえる。
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