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協調鉄ニトロシルに対するヒドリド攻撃:ヘムモデル-HNO誘導体の形成のための実験的およびDFTの証拠

Erwin G Abucayon¹, Rahul L Khade², Douglas R Powell¹

¹Department of Chemistry and Biochemistry, University of Oklahoma , Norman, Oklahoma 73019, United States.

Journal of the American Chemical Society

|December 19, 2015

まとめ

研究者は新しい鉄ヘム-ニトロシル水素 (Fe-HNO) モデル化合物を合成した. この突破は,これらの中間物質を含む生物学的プロセスを理解するために不可欠な最初の明確に定義されたFe-HNO種を提供します.

科学分野:

バイオ有機化学
有機金属化学
スペクトロスコーピー

背景:

ヘム・ニトロシル水素 (HNO) 種は,多くの生物学的経路において重要な中間物質である.
明確に定義された鉄 (Fe) ヘム-HNOモデル化合物の合成と特徴付けは,この分野において重要な課題である.

研究の目的:

最初の明確に定義されたFe-heme-HNOモデル化合物を合成し,特徴づけること.
鉄性ニトロシル複合体に対するヒドリド攻撃のメカニズムを解明する.

主な方法:

オクタエチルポルフィリナートリガンドと5-メチリミダゾールによるカチオン鉄化合物の合成.
赤外線 (IR) とプロトン核磁気共鳴 ((1) H NMR) スペクトロスコーピーを用いた特徴付け.
反応機構を調査するための密度関数理論 (DFT) の計算.

主要な成果:

ハイドリッド攻撃によるFe-HNO製品の生成と特徴付けに成功した.
光譜データ (IRと (1) H NMR) は,Fe-HNO種の形成を確認した.
DFTの計算は,調整されたニトロシルリガンドの窒素原子に直接の水素攻撃を示した.

結論:

この研究は,初めて明確に定義されたFe-heme-HNOモデル化合物を報告した.
この発見は,Fe-HNO中間物質の反応性と構造に関する重要な洞察を提供します.
この研究は,ヘム-HNO種の生物学的役割に関するさらなる調査のための基礎を築く.

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