熱的に惰性なサイクロメタラテッドル (ru) の光化学解像度
Lucien N Lameijer1, Corjan van de Griend1, Samantha L Hopkins1
1Leiden Institute of Chemistry, Leiden University , Einsteinweg 55 , 2333CC Leiden , The Netherlands.
Journal of the American Chemical Society
|December 12, 2018
まとめ
この研究では,キラルな有機金属ルテニウム (II) 複合体を分離するための新しい光置換法が導入されています. この光化学的戦略は,ダイアステレオイソメアの分離を可能にし,キラル複合体の合成のための新しい合成経路を提供します.
科学分野:
- 有機金属化学
- 写真化学
- チラルの合成
背景:
- チラルの有機金属複合体は,触媒と材料科学において極めて重要です.
- 熱リガンド交換のようなキラル複合体の解消のための伝統的な方法は,結合惰性のためにしばしば無効である.
- ルテニウム ((II) サイクロメタラテッド複合体は,フェニル-バイピリジルリガンドでユニークな構造および光化学的性質を呈する.
研究 の 目的:
- キラルな有機金属複合体の分離のための光置換戦略を開発する.
- チラルサイクロメタレットルテニウム (II) コンプレックスの一連の合成と特徴付け.
- これらの複合体の光化学的振る舞いを調査し,光置換に影響を与える要因を理解する.
主な方法:
- 5つのサイクロメタル化ルテニウム ((II) 複合体の合成と特徴付け: Ru ((phbpy)) ((N-N)) ((DMSO-κS)) ((PF6).
- アセトニトリルで可視光照射によって誘発される光置換反応.
- キラル硫化物の熱調整を用いたキラル解像度,その後に逆相HPLCによるダイアステレオイソメアの分離.
主要な成果:
- 合成された5つの複合体のうち3つ ([1]PF6-[3]PF6) は選択的光置換を受けた.
- ダイアステレオイソメアのキラル解像度は,光化学的方法によって特定の複合体で成功しました.
- 光化学的,電気化学的,および境界軌道分析は,複合体間の異なる光化学的惰性を説明した.
結論:
- 光置換は,キラルな有機金属複合体を解消するための熱的方法の有効な代替手段を提供します.
- この光化学的アプローチは,エナティオメリカルに純粋なサイクロメタル化ルテニウム (II) 複合体の合成のための新しい経路を提供します.
- 光置換を制御する電子的および構造的要因を理解することは,新しいキラル複合体の設計の鍵です.
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