IF 2.2 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR
Parkhi Sharma, Rakesh Kumar, Ayushi Awasthi, Apparao Draksharapu
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引用次数: 0

摘要

在非血红素铁酶中观察到的特殊反应性可归因于它们在活性位点获得高价铁氧物种的能力。迄今为止,已有大量无机模型络合物被报道,使我们得以深入了解许多含铁酶的复杂结构和光谱特征,并加深了我们对其酶反应途径的理解。虽然已使用各种氧化剂对合成铁络合物的反应活性进行了评估,但对反应中间体形成的研究主要集中在乙腈上。然而,作为生物系统介质的水却较少被用于这些研究。有鉴于此,我们利用各种氧化剂,在水中用模型复合物 [(BnTPEN)Fe(II)(OTf)]+ (1)(其中 BnTPEN=N-benzyl-N,N,N-tris(2-pyridylmethyl)-1,2-diaminoethane )对关键活性物种的生成进行了全面研究,并取得了重要发现。在水中,使用氧化剂 NaIO4 可以定量生成 Fe(IV)=O 物种。此外,我们还观察到了侧向 Fe(III)-OO 和 Fe(III)-OOH 之间的平衡,后者最终转化为 Fe(IV)=O。从这项研究中获得的启示很可能与其他具有多吡啶基五正齿配体的 Fe(II) 复合物的化学相关。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Exploring the Reactivity of High Valent Iron Intermediates in Water

Exploring the Reactivity of High Valent Iron Intermediates in Water

The exceptional reactivity observed in non-heme iron enzymes can be attributed to their capability to access high-valent iron oxygen species in their active site. Numerous inorganic model complexes have been reported to date, providing insights into the intricate structural and spectroscopic features of many iron-containing enzymes and advancing our understanding of their enzymatic reaction pathways. While the reactivities of synthetic iron complexes have been evaluated using various oxidants, the investigation into the formation of reactive intermediates has primarily focused on acetonitrile. However, water, which serves as the medium in biological systems, has been less frequently employed in these studies. Motivated by this, we conducted a comprehensive study on the generation of key reactive species using various oxidants with a model complex, [(BnTPEN)Fe(II)(OTf)]+ (1) (where BnTPEN=N-benzyl-N,N,N-tris(2-pyridylmethyl)-1,2-diaminoethane) in water, which yielded important findings. In water, a quantitative yield of Fe(IV)=O species was achieved with the oxidant NaIO4. Additionally, we observed an equilibrium between side-on Fe(III)−OO and Fe(III)−OOH, with the latter eventually converting to Fe(IV)=O. The insights gained from this study are likely to be relevant in the chemistry of other Fe(II) complexes with polypyridyl pentadentate ligands.

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来源期刊
European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
4.30
自引率
4.30%
发文量
419
审稿时长
1.3 months
期刊介绍: The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.
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