TPAリガンドを含む分子バスケットと亜鉛のロシア産巣人形複合体
Lei Zhiquan1, Shane Polen1, Christopher M Hadad1
1Department of Chemistry and Biochemistry, The Ohio State University , 100 West 18th Avenue, Columbus, Ohio 43210, United States.
Journal of the American Chemical Society
|June 16, 2016
まとめ
この研究は 分子バスケットが 金属複合体を封じ込み 新しい構造を作り出すことを示しています エナチオピュアバスケットはキラリティを移転し,トリス2-ピリジルメチル) アミン (TPA) 金属複合体の新しい触媒およびキラル差別アプリケーションを可能にします.
科学分野:
- 超分子化学
- 協調化学
- チラルの認識
背景:
- Tris ((2-ピリジルメチル) アミン (TPA) 金属複合体は,触媒作用において重要である.
- 金属の複雑な性質を制御するための 分子構造の設計は 重要な課題です
- 第2の調整球の相互作用は反応性と選択性に影響を与える.
研究 の 目的:
- の分子バスケット内のZn (II) -TPA複合体の複合性を調査する.
- エナチオプアバスケットから 封装された金属複合体へのキラリティの移転を 探求する.
- TPA複合体の触媒機能の強化とキラル差別の可能性を評価する.
主な方法:
- 凸のZn(II) -TPA複合体 (1) と凸のバスケット (2と3) の合成と特徴付け
- 核磁気共振 (NMR) スペクトロスコーピーと質量スペクトロメトリにより,複合体の形成を確認する.
- クイラル移転と構造変化を研究するための円形の二重化 (CD) スペクトロスコーピー.
主要な成果:
- バスケット2はZn(II) -TPA複合体 (1) を水に閉じ込め,結合定数 (2.0 ± 0.2) × 10(3) M(-1の1:1複合体を形成した.
- (S) - アラニンで機能化されたエナンチオピュアバスケット3は,その静的キラリティをカプセル化されたZn (II) - TPA複合体に転送した.
- このキラル移転は,分子間イオン接触を通じて,TPAリガンドのピリジン環に左手 (M) 螺旋の回転を誘導した.
結論:
- 分子バスケットは,金属を含むTPAの第2の調整球として効果的に機能します.
- エナティオプアバスケットは,アキラル金属複合体にキラル性を与え,キラルプロペラにつながります.
- これらの発見は,TPAベースのシステムの触媒およびキラル識別能力を高めるための経路を提供します.
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