合成鉄・硫黄・炭素基体の窒素素関連反応性
Amy L Speelman1, Ilija Čorić1, Casey Van Stappen2
1Department of Chemistry , Yale University , 225 Prospect Street , New Haven , Connecticut 06520 , United States.
Journal of the American Chemical Society
|August 13, 2019
まとめ
合成鉄-硫黄-炭素複合体は窒素酵素の活性を模倣し,窒素 (N2) を結合させ,アンモニアとヒドラジンに還元する. 触媒的還元における課題は,将来のバイオミメティック・コンプレックス・デザインの分野を強調しています.
科学分野:
- バイオ有機化学
- 有機金属化学
- カタリシス
背景:
- 窒素酵素は,窒素 (N2) の固定のために鉄モリブデン共因子 (FeMoco) の活性部位を利用する.
- 硫黄 (S) と炭素 (C) のドナーを持つ単純な合成化合物は,FeMocoの結合環境を模倣することができます.
- 以前に,N2結合はSとCドナーで単核鉄部位で達成された.
研究 の 目的:
- 合成鉄 - 硫黄 - 炭素システムにおけるN2結合のメカニズムを調査する.
- N2の調整と還元における鉄酸化状態の役割を理解する.
- N2をアンモニアとヒドラジンに還元する可能性をバイオミメティックサイトで探求する.
主な方法:
- 鉄 (III) トリス (III) チオラート複合体の合成
- KC8を用いた電気化学的還元
- Mössbauer,EPR,X線吸収スペクトロスコーピーを含むスペクトロスコーピーの特徴.
- 密度関数理論 (DFT) の計算
- N2と弱い酸と反応する
主要な成果:
- 硫黄の調整を保持した鉄 (S=3/2) 種への減少が観察された.
- 鉄へのさらなる還元は,チオラート解離とN2結合を誘導した.
- 鉄−I状態に還元され,その後,酸と反応してアンモニアとヒドラジンが得られる.
- 触媒によるN2還元は,リガンドのプロトン化と解離により失敗した.
結論:
- このシステムにおけるN2結合と還元は,鉄 (I) 状態を超えて鉄 (I) と鉄 (I) に還元する必要があります.
- 合成Fe-S-Cサイトは,N2から窒素化製品 (アンモニア,ヒドラジン) を生成することができる.
- リガンドの安定性は,将来のバイオミメティック複合体の設計のための洞察を提供する,触媒的なN2削減を達成するために不可欠です.
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