モリブデンオキシベンジリデン複合体の合成
Feng Zhai1, Konstantin V Bukhryakov1, Richard R Schrock1
1Department of Chemistry 6-331 , Massachusetts Institute of Technology , Cambridge , Massachusetts 02139 , United States.
Journal of the American Chemical Society
|October 9, 2018
まとめ
この研究は,新しいモリブデンアルキリデンおよびベンジリデン複合体の合成と特徴を詳細に説明する. これらのオルガノモリブデン化合物は,水とオレフィンとのユニークな反応性を示し,新しい触媒中間物質を形成します.
科学分野:
- 有機金属化学
- モリブデン触媒
- 協調化学
背景:
- モリブデン複合体は,様々な触媒変換において重要な役割を果たします.
- モリブデンアルキリデンおよびベンジリデン複合物の反応性を理解することは,新しい合成方法論の開発の鍵です.
- 以前の研究では関連系を調べたが,重量のあるリガンドと小分子による特定の反応パターンは依然として興味のある分野である.
研究 の 目的:
- 新しいモリブデン (VI) ベンジリデンとアルキリデンの複合体を大量結合体で合成し,特徴づけること.
- これらの複合体の水とオレフィンとの反応性を調査する.
- 観察された変換の構造的および機械的側面を明らかにする.
主な方法:
- リチウムアミド塩基とフォスフィンとの反応によるモリブデン複合体の合成
- 重要な中間物質の構造的決定のためのX線結晶学.
- 核磁共振 (NMR) スペクトロスコーピーは,特徴と反応のモニタリングのために使用されます.
- オレフィン挿入を研究するために,エチレンおよびノルボナディエン誘導体との反応.
主要な成果:
- トリゴナルバイピラミダル抗ベンジリデン複合体の合成 Mo(O) ((CHAro) ((OHMT) 2.
- 水との反応で二重ヒドロキシブリッジ複合体の形成.
- 各種フォスフィンの複合体であるMo (O) (CHArp) (ORF9) 2 (L) を生成した.
- 4座標のシンアルキリデン複合体を合成した Mo(O) ((CHArp) ((OHMT) 2.
- メタラサイクロブタン形成とオレフィンメタテシスの中間物質につながるエチレンとの観察反応.
- ノルボナディエン誘導体による最初の挿入製品の合成を報告した.
結論:
- OHMTリガンドのステリック塊は,モリブデン複合体の幾何学と反応性に影響する.
- 合成されたモリブデン複合体は,触媒的に関連する種の前駆体として機能する.
- この研究は,高値モリブデンアルキリデンの不飽和基質との基本的な反応性についての洞察を提供します.
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