可視光を用いたサイクロメタラ化プラチナのトリプル興奮状態における芳香C-H活性化
Fabio Juliá1, Pablo González-Herrero1
1Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia , Apartado 4021, 30071 Murcia, Spain.
Journal of the American Chemical Society
|April 9, 2016
まとめ
この研究は,プラチナ (II) 複合体の可視光駆動サイクロメタレーションを報告している. このプロセスは,前例のないC-H酸化添加によって新しいホモレプティックおよびヘテロレプティックプラチナ複合体を生成します.
科学分野:
- 有機金属化学
- 写真化学
- カタリシス
背景:
- サイクロメタレーションは有機金属化学における重要な反応である.
- プラチナ (II) 複合体は,触媒と材料科学で広く使用されています.
- 可視光光化学は 持続可能な合成経路を提供します
研究 の 目的:
- プラチナ (II) コンプレックスによる可視光によるサイクロメタレーションを報告する.
- ホモレプティックとヘテロレプティックプラチナ複合体を合成する
- C−Hの酸化添加のメカニズムを解明する.
主な方法:
- 室温で青いLEDを用いた光化学反応
- [PtMe (C^N) (N^CH) ]型のプラチナ ((II) の前駆体合成
- 反応メカニズムを調査するための実験的および計算的研究 (DFT).
主要な成果:
- [PtMe ((C^N)) ((N^CH)) ]の前駆体に対する可視光照射により,ホモレプス性cis-[Pt ((C^N)) 2複合体が生じる.
- [PtMe((N'^C'H) ]前駆体からヘテロレプティックなcis-[Pt(ppy) ((C'^N') ]複合体の合成.
- 金属からリガンドへの電荷移転 (MLCT) 文字のトリプル興奮状態のC-H酸化添加を開始する.
- Pt (IV) メチルヒドリドの中間物質の検出
結論:
- 可視光光化学は,プラチナ (II) 複合体の効率的なサイクロメタレーションを可能にします.
- この反応は前例のないC−H酸化加減機構によって進行する.
- この作業は,穏やかな条件下でプラチナ複合体の合成有用性を拡大します.
関連する概念動画
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Removing one hydrogen from the intervening CH2 group...
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