鉄-イミド種の特徴化 N群移転化学に係る
Diana A Iovan1, Theodore A Betley1
1Department of Chemistry and Chemical Biology, Harvard University , 12 Oxford Street, Cambridge, Massachusetts 02138, United States.
Journal of the American Chemical Society
|January 21, 2016
まとめ
この研究では,アリルアジドと反応し,末端または橋渡しイミド種を形成する新しい鉄複合体を合成しました. これらの鉄イミド複合体は,N-グループ転送反応とC-Hアミネーションの触媒として潜在性を示しています.
科学分野:
- 有機金属化学
- 協調化学
- キャタリシス
背景:
- 鉄の複合体は様々な触媒的変換に不可欠です.
- 鉄イミド種の反応性を理解することは,新しい触媒システムの開発の鍵です.
- ステリカルに阻害されたリガンドは,金属複合体の安定性と反応性に影響を与える.
研究 の 目的:
- 新型テルト-ブチル-置換型ディピルナート・ディ-鉄 (II) 複合体を合成し特徴づけること.
- 鉄イミド種を形成するアリルアジドとのこれらの複合体の反応性を調査する.
- N-グループ移転とC-Hアミネーション反応における生成鉄イミド複合体の触媒的可能性を調査する.
主な方法:
- テルトブチル置換型ディピルナトジ鉄 (II) 複合体の合成
- 様々なアリルアジドと反応して,終末と橋渡し鉄イミド複合体を形成する.
- (57) 構造的および電子的特徴化のためのメスバウアー光譜とX線結晶学.
- SQUID磁気測定と固体磁気測定で磁気特性を測定する.
- 触媒介質を観察するための現地監視
主要な成果:
- ステリカルで利用可能なテルブチル置換型ディピルナト二鉄 (II) 複合体の合成に成功した.
- アリルアジド構造に応じて,末端の鉄イミニルと橋渡しの二鉄イミドの2つの異なる鉄イミド産物の形成.
- 高スピンのFe (III) センターを含む鉄イミド種の電子構造と磁気特性の特徴.
- 橋渡しダイ鉄イミドが,C−Hアミネーションにおける有能なN群転移反応剤と,触媒的に活性な種であることを示す.
結論:
- 合成された鉄複合体は,調整可能な反応性を持つ多様な鉄イミド種にアクセスできます.
- 橋渡しの二鉄イミド複合体は,HAAとN群転移反応において触媒的活性を示している.
- これらの発見は,有機合成における汎用的な触媒としての鉄イミド複合体の可能性を強調しています.
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