非無害なリガンドを用いた二水素のレドックス交換酸化
Mark R Ringenberg1, Swarna Latha Kokatam, Zachariah M Heiden
1Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
Journal of the American Chemical Society
|January 1, 2008
まとめ
この研究では,水素を活性化する酸化還元交換可能な有機金属イリジウム複合体を導入しています. 酸化により水素の活性化が可能になり,H2の酸化のための新しい触媒経路を示しています.
科学分野:
- 有機金属化学 有機金属化学
- カタリシス カタリシス カタリシス
- 無機化学 無機化学とは
背景:
- 有機金属複合体の非無害なリガンドは,ユニークな反応性を提供します.
- 水素の活性化は,触媒とエネルギー変換の重要なプロセスです.
研究 の 目的:
- 非無害なリガンドを用いた新しいCp*Ir複合体を合成し,特徴づけること.
- これらの複合体のリドックス交換可能な水素活性化能力を調査する.
主な方法:
- Cp*Ir(tBAFPh) コンプレックス (1) の合成
- 電気化学的酸化と酸化された種の特徴 [1]+.
- ステリカルに阻害された塩基の存在下でのH2活性化の運動学的研究.
主要な成果:
- 複合体1 (16e-) は,モノカチオン [1]+に酸化されるまで無効である.
- 酸化はリガンド中心であり,結晶学,EPR,および元素分析によって確認されています.
- モノカチオン [1]+は,リドックス・スイッチ可能なメカニズムを通じてH2の活性化を触媒化する.
結論:
- Cp*Ir(tBAFPh) システムは,リドックス交換可能なH2活性化を示しています.
- 触媒は単離性種によって促進され,リガンド中心の酸化還元活性が果たす役割を強調しています.
- [1]+へのMeCNの調整は触媒を阻害し,調整球に対する感受性を示す.
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