テトラ核鉄複合体における推定末端オクソ種による分子内C-HとC-F結合の酸素化
Graham de Ruiter1, Niklas B Thompson1, Michael K Takase1
1Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Journal of the American Chemical Society
|January 14, 2016
まとめ
テトラ核鉄複合体は,分子内アレンC-HとC-F結合の酸素化を達成する. この研究は,C−O結合形成のための異なる反応経路を示唆するFe−oxo中間体による地域選択的水酸化を明らかにしている.
科学分野:
- 無機化学
- 有機金属化学
- カタリシス
背景:
- 鉄複合体は様々な触媒性酸化反応において極めて重要です.
- C-HとC-F結合の活性化を理解することは,合成化学の鍵です.
- テトラ核クラスターは,反応性のためにユニークな電子と構造的特性を提供します.
研究 の 目的:
- 四核鉄複合体を用いて分子内アレンのC-HとC-F結合の酸化を調査する.
- これらの鉄のクラスターによって媒介される地域選択的水酸化のメカニズムを解明する.
- Fe-oxo 中間物質と潜在的な電子転送経路の役割を探求する.
主な方法:
- テトラ核鉄複合体 ([LFe3(PhPz) 3OFe][OTf]2およびそのフッ化アナログ) の合成と特徴づけ
- 鉄複合体がヨドソベンゼンと反応し,C-HとC-F結合の酸素化を誘導する.
- 反応産物の分析により,地域選択性を決定し,中間産物を特定する.
主要な成果:
- 橋渡しピラゾラートリガンドの地域選択的水酸化が達成され,C-HまたはC-F結合からC-O結合が形成された.
- 反応性は,末端および反応性鉄酸化物 (Fe-oxo) 中間物質の関与を示唆する.
- クラスター内の潜在的分子内電子移転が,反応経路に影響を及ぼすという証拠がある (Fe ((IV) -オクソとFe ((III) -オクソ).
結論:
- テトラ核鉄複合体は,分子内アレンC-HとC-F結合の酸素化を効果的に媒介することができる.
- この研究は,フェオキソ中間物質の形成とC−O結合形成におけるその役割を強調している.
- 観測された水酸化には,異なる鉄酸化状態を含む異なる反応機構が提案されている.
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