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 |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Hirosaki University |
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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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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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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 / メタラサイクル / シライミン / ホスファシレン / 有機金属錯体 / 小分子活性化 / 有機金属化学 |
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| 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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| 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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Report
(5 results)
Research Products
(42 results)
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[Journal Article] Synthesis and photophysical properties of azuleno[1′,2′:4,5]pyrrolo[2,1-b]quinazoline-6,14-diones: Azulene analogs of tryptanthrin2018
Author(s)
Chieko Kogawa, Asuka Fujiwara, Ryuta Sekiguchi, Taku Shoji, Jun Kawakami, Masaaki Okazaki, Shunji Ito*
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Journal Title
Tetrahedron
Volume: 74
Issue: 49
Pages: 7018-7029
DOI
Related Report
Peer Reviewed
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[Journal Article] Directed ortho-C-H Silylation Coupled with trans-Selective Hydrogenation of Arylalkynes Catalyzed by Ruthenium Complexes of a Xanthene-Based Si,O,Si-Chelate Ligand, “Xantsil”2016
Author(s)
Takashi Komuro, Takeo Kitano, Nobukazu Yamahira, Keisuke Ohta, Satoshi Okawara, Nathalie Mager, Masaaki Okazaki, Hiromi Tobita
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Journal Title
Organometallics
Volume: 印刷中
Issue: 9
Pages: 1209-1217
DOI
Related Report
Peer Reviewed / Acknowledgement Compliant
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