ウラニルβ-ケトイミナート複合体におけるオクソリガンドシリレーション
Jessie L Brown1, Guang Wu, Trevor W Hayton
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
Journal of the American Chemical Society
|May 13, 2010
まとめ
トリメチルシリルヨウ酸化物 (Me3SiI) はウラニル複合体と反応して,新しいウラン化合物を形成する. この反応経路は,他のトリメチルシリルハリドを含む反応と著しく異なるため,有機金属化学におけるユニークな反応性を強調しています.
科学分野:
- 有機金属化学 有機金属化学
- ウラン化学 ウラン化学
- シリコン化学 シリコン化学
背景:
- 巨大ベータ-ディケチミネートリガンド (Ar) アクナックを含むウラニル複合体は,その反応性について研究されています.
- シリアリング剤がウランの調整環境を変更する役割は,重要な関心分野です.
研究 の 目的:
- ウラニル複合体のトリメチルシリルヨウ酸化物 (Me3SiI) との反応を調査する.
- ウラニル複合体に対するMe3SiIと他のトリメチルシリルハリド (Me3SiX,X=Cl,OTf) の反応性を比較する.
主な方法:
- ウラニル複合体のUO2とMe3SiI.との反応
- 反応産物の分離と特徴づけ.
- Me3SiClとMe3SiOTfを含む反応を比較した研究.
主要な成果:
- Me3SiIをUO2 ((((Ar) acnac) 2に加えると,適度な収量で U(OSiMe3) 2I2 (((((Ar) acnac) が得られる.
- 副産物には,I2と,Me3Si+抽出から生じる,シライ化リガンドであるArNC(Ph) = CHC(Ph) OSiMe3が含まれています.
- Me3SiClとMe3SiOTfとの反応により,それぞれ異なるウラニル複合体,UO2Cl2 ((((Ar) acnacH) 2とUO2 (((OTf) 2 ((((Ar) acnacH) 2 (((Et2O) が生成されます.
結論:
- Me3SiIは,ウラニル複合体を持つMe3SiClおよびMe3SiOTfと比較して明確な反応性を表しています.
- Me3SiIとの反応経路は,ウラニル酸素のシル化とリガンド抽出を含む.
- トリメチルシリルハリドの選択は,ウラニルβ-ディケチミナート複合体との反応の結果に大きな影響を与えます.
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