非血红素铁配合物中二次球形氢键对氧反应性的影响。

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2025-02-12 Epub Date: 2025-02-02 DOI:10.1021/jacs.4c15153

Andrew R LaDuca, Jessica R Wilson, Writhabrata Sarkar, Matthias Zeller, Nathaniel K Szymczak

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引用次数: 0

摘要

非血红素铁配合物携带三（6-苯基-吡啶基）甲胺（TPANHPh）配体和附加氢键（h -键）基团，表现出容易的氧反应性，形成单体Fe(III)OH配合物，该配合物可以通过反弹到碳自由基上释放•OH。以三（6-甲基吡啶基）甲胺（TPAMe）为基料，无氢键的类似化合物表现出极小的氧反应性，形成Fe(III)2(μ-O)（μ-OH）二聚体，也与碳基自由基反应。h键系统使O2结合和激活弱还原非血红素铁配合物，突出了次级球单元在非典型氧化还原环境中促进反应的协同作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Impact of Secondary Sphere Hydrogen Bonds on O₂ Reactivity within a Nonheme Iron Complex.

A nonheme iron complex bearing the tris(6-phenylamino-pyridyl)methylamine (TPA^NHPh) ligand with appended hydrogen bond (H-bond) groups displays facile O₂ reactivity to form a monomeric Fe(III)OH complex, which can release •OH via rebound to a carbon radical. An analogous compound without H-bonds, based on tris(6-methylpyridyl)methylamine (TPA^Me), exhibits minimal O₂ reactivity, forming a Fe(III)₂(μ-O)(μ-OH) dimer, which also reacts with carbon-based radicals. The H-bonding system enables O₂ binding and activation at weakly reducing nonheme iron complexes, highlighting a cooperative role of secondary sphere units to facilitate reactions at atypical redox environments.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.