アリルナイトレノイドブリッジデコッパー複合体の電子構造と反応性プロファイル
Kurtis M Carsch1, James T Lukens2, Ida M DiMucci2
1Department of Chemistry and Chemical Biology , Harvard University , 12 Oxford Street , Cambridge , Massachusetts 02138 , United States.
Journal of the American Chemical Society
|January 10, 2020
まとめ
パックマン・ディピリン・リガンドによるディコッパー複合体は合成され,減少した. 発生したイミド複合体は,C-Hアミネーションのような,ラジカル誘発反応を可能にする,NAr局所化されたスピンを表す.
科学分野:
- 協調化学
- 有機金属化学
- キャタリシス
背景:
- ディコッパー複合体をテンプレートするのに有効である.
- 中性イミド複合体 (Rdmx) Cu2 ((μ2-NAr) の合成には,ジクプロス前駆体とアリルアジドが含まれている.
研究 の 目的:
- 新しい二銅イミド複合体を合成し,特徴づけること.
- 電子構造と減少した二銅イミドとイミニル複合体の反応性を調査する.
- C-H アミネーション,窒素移転,H原子抽出を含む,激素誘発反応性を探求する.
主な方法:
- デプロトン化/金属化またはトランスメタル化による二銅複合体の合成.
- イミド複合体の減少は,カリウムグラフィートまたは他の化学的減少剤を使用します.
- EPR,X線吸収 (Cu L2,3/K-エッジ,N K-エッジ),光学スペクトル検定を含むスペクトル検定.
- DFT/CASSCF計算を用いた計算分析
主要な成果:
- 中性イミド複合体 (Rdmx) Cu2 ((μ2-NAr) が成功して合成された.
- 特定の複合体の1電子還元により,分子内ベンジルC-Hアミネーションが開始される.
- 化学的還元により,分離可能なイミニル複合体 [{Rdmx) Cu2{μ2-NAr) ]− が得られた.
- 還元された複合体は,正式にはClass IIIA混合バレンスのもので,有意なNAr局所化スピンを有する.
- 反応性は,アリル置換剤によって影響され,N-ラジカル特性に影響する.
結論:
- 減少した二銅イミド複合体は,ユニークな電子構造と反応性を示す.
- 縮小された複合体におけるNAr局所化されたスピンは,根幹が促進する変異を容易にする.
- アリル置換剤は,これらの複合体のN-ラジカル特性と反応性を調節する上で重要な役割を果たします.
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