非ヘム鉄 (IV) -オクソ複合体による選択的酸素原子移転が劇的に加速:第1回目と第2回目調整球のチューニング
Leland R Widger1, Casey G Davies, Tzuhsiung Yang
1Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
Journal of the American Chemical Society
|January 30, 2014
まとめ
硫化物リガンドを含む新しい鉄 (II) 複合体は,酸素原子移転反応を迅速に可能にします. この研究は,複雑な詳細を詳しく述べています.
科学分野:
- バイオ・オーガニック化学 バイオ・オーガニック化学
- 有機金属化学 有機金属化学
- 協調化化学について
背景:
- 鉄複合体は,様々な酸化反応における重要な触媒である.
- 鉄の反応性を調節するリガンド環境の役割を理解することが鍵となる.
- 新種のリガンドの開発は,新しい触媒経路を開くことができます.
研究 の 目的:
- 硫化リガンドを含む新しい鉄 (II) 複合体を合成し,特徴づけること.
- 酸素原子移転 (OAT) 反応における鉄複合体の反応性を調査する.
- OATメカニズムに対するリガンド構造の影響を調査する.
主な方法:
- 新しいN3Py (アミド) SRリガンドとそのFe (II) 複合体の合成.
- Fe(II) 複合体とその酸化したFe(IV) 中間物質の特徴.
- H-結合相互作用を確認するためのスペクトロスコピーと構造分析.
- 様々な基板でのOAT活性を評価するための運動学的研究.
主要な成果:
- 新しいFe(II) 複合体である[Fe(II) ((N3Py ((アミド) SR) ] ((BF4) 2 (1) が合成されました.
- メタスタブルなFe ((IV) -オクソ種[Fe ((IV) ((O) ((N3Py ((アミド)) SR) ] ((2+) (2) が生成され,近隣のアミドH結合ドナーが特徴でした.
- コンプレックス2は,外部硫化物基板への迅速なOATを示した.
- 直接のS酸化が達成され,硫黄酸化結合複合体である[Fe (II) ][N3Py (N3Py) ][S (O) ][R (R) ][BF (BF4) ]2 (4) を生成した.
- 複合体1のOATの触媒活性が観察されました.
結論:
- 新型リガンドN3Py(アミド) SRは,反応性鉄酸化状態を効果的に安定させます.
- アミドH結合ドナーの近接は,Fe (IV) -オクソ種の反応性に影響する.
- 鉄複合体は,酸化反応,特にS-酸化反応の触媒としての潜在能力を示しています.
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