Development of Transformations of Inert Bonds Catalyzed by Chelate Complexes Involving Silyl Coordinating Moieties
| Project/Area Number |
16K05714
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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 | Tohoku University |
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Principal Investigator |
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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: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
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| Keywords | 金属錯体 / シリル配位子 / キレート配位子 / 配位子設計 / 触媒 / C-H結合活性化 / 官能基化 / 小分子活性化 / N-複素環式カルベン / 重水素化 / 遷移金属錯体 / 支持配位子 / 窒素配位子 / 触媒反応 / ボリル化 / ピンサー配位子 / C-D結合活性化 / H/D交換 / 合成化学 / 触媒・化学プロセス |
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| Outline of Final Research Achievements |
To develop catalysts for transformations of inert bonds such as carbon-hydrogen (C-H) bonds under mild conditions, we investigated synthesis and catalysis of newly-designed metal complexes bearing chelate ligands involving silyl coordinating moieties bound to metals via silicon. As representative results, silyl chelate complexes of late transition metals (iridium and ruthenium) were found to catalyze the following reactions: (1) Si-H deuteration of trialkylsilanes with benzene-d6 via activation of its carbon-deuterium (C-D) bonds, (2) C-H borylation of aromatic compounds, (3) hydrosilylation of carbon dioxide, and (4) C-H deuteration of trialkylphosphine via H/D exchange with benzene-d6.
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| Academic Significance and Societal Importance of the Research Achievements |
本研究では，新しいシリルキレート配位子を持つ金属錯体の合成手法を確立するとともに，それら錯体が不活性なC-H結合や二酸化炭素分子を温和な条件下(室温～60 ℃)で変換する高性能な触媒として働くことを実証したことで，学術的に独自性と新規性の高い成果が得られたといえる。特に有機化合物のC-H結合を直接変換する反応は，医薬品や化成品などの有用物質の製造手法に活用できると期待されているため，その反応を促進する触媒を開発する意義が大きい。
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Report
(4 results)
Research Products
(29 results)
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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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