アルカリ金属で覆われたセリウム (IV) イミド複合体
Lukman A Solola1, Alexander V Zabula1, Walter L Dorfner1
1P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
Journal of the American Chemical Society
|May 11, 2016
まとめ
研究者は新しいリガンド戦略を用いて最初の終端セリウム-窒素多重結合を合成した. この突破により 安定した,高度に反応するセリウム-窒素結合が実現し ランタナイド化学を進める中で 最も短い結合となった.
科学分野:
- 有機金属化学
- ランタニド化学
- 非有機合成
背景:
- ターミナル・ランタニド・リガンドの多重結合は,予想される高い反応性と弱度の軌道重複により,極めて稀である.
- 過去の戦略では 負荷の偏化と不安定性のために これらの種を隔離するのに苦労しました
研究 の 目的:
- 安定した末端ランタニド-リガンド多重結合を分離するための新しい戦略を開発する.
- 終端のセリウム-窒素多重結合複合体を合成し,特徴づけること.
主な方法:
- ステリックと電子的な保護のために,特製のTris (ヒドロキシラミネート) リガンドのフレームワーク,TriNOx (トリノックス) を使用した.
- 合成に使用されたセリウム (IV) 複合体.
- X線結晶学を用いて結果の複合体を特徴づけた.
主要な成果:
- 最初の正式な終端セリウム-窒素 (CeN) 多重結合を成功裏に分離した.
- 合成された複合体[K(DME) 2[CeN(3,5-(CF3) 2C6H3) ((TriNOx) ]は,最も短いCeN結合長さである2.119(3) Åを示している.
- TriNOx3-) リガンドフレームワークは,リガンドのスクランブル化,オリゴメリゼーション,還元を防止した.
結論:
- セリウム (IV) とトリノックス (TriNOx) 3−) リガンドを用いた開発された戦略は,末端ランタニドリガンド多重結合の分離に有効である.
- この研究は,ランタニドの既知の化学を拡張し,高度に反応する複数の結合を安定させる可能性を実証した.
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