2019 Fiscal Year Final Research Report
Creation of heterobimetallic complexes utilizing hybrid-type NHC ligand for development of cooperative reaction site
| Project/Area Number |
17K05805
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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 | Yokohama National University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
橋本 徹 横浜国立大学, 大学院工学研究院, 助教 (90710898)
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| Project Period (FY) |
2017-04-01 – 2020-03-31
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| Keywords | 金属錯体触媒 / ニッケル錯体 / モノアニオン性3座ピンサー型配位子 / 不活性結合活性化 / クロスカップリング反応 / ヒドロホウ素化反応 / 鉄塩錯体 |
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| Outline of Final Research Achievements |
Systematic synthesis of nickel complexes bearing a monoanionic tridentate pincer-type ligand and the catalytic ability of these complexes were investigated. Cross-coupling reactions using aryl Grignard reagents as nucleophiles were examined. In cases of aryl chlorides and -fluorides as electrophiles, the O,N,P- and N,N,P-pincer-type nickel complexes acted as effective catalysts for the coupling reaction. Using allylic ethers, the relatively robust C-O bond cleavage occurred to afford corresponding allylbenzene derivatives in good to excellent yields. Furthermore, the O,N,P-nickel complex acted as an effective catalyst for the highly Markovnikov-selective hydroboration of vinylarenes using bis(pinacolate)diboron.
Bis(triphenylphosphoranylidene)ammonium tetrachloroferrate, (PPN)[FeCl4], exhibited high stability toward air and moisture and acted as an effective catalyst for the cross-coupling reaction of secondary alkyl bromides with aryl Grignard reagents.
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| Free Research Field |
錯体化学，有機金属化学
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| Academic Significance and Societal Importance of the Research Achievements |
有機化合物の特定の結合切断を伴う新たな結合生成反応や炭素－炭素二重結合などの不飽和結合に対する有機基質の選択的な付加反応を実現する金属錯体触媒の開発は新たな有機合成の方法論を構築するうえで重要な課題である。さらに，金属錯体に主眼を置いた触媒開発研究は錯体化学のみならず有機合成化学において重要は情報を提供できる。金属錯体触媒を用いた新たな方法論の開発は，省エネルギープロセスの開発に寄与するだけでなく，持続可能な物質社会を永続的に発展させるための重要な課題である。本研究で開発したニッケル錯体はこれらの基礎研究に資するものであり，関連分野への波及効果が期待できる。
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