反应性(心理学)
化学
氢化物
烯烃
光化学
烷基
铁质
药物化学
铁
氢
无机化学
催化作用
有机化学
医学
病理
替代医学
作者
Hao Jiang,Wenzhen Lai,Hui Chen
标识
DOI:10.1021/acscatal.9b01691
摘要
Iron-hydride and alkene constitute a promising pair of reactants to access alkyl carbon radicals. However, the fundamental mechanistic scenario remains unclear. High-level coupled cluster calculations reported in this work demonstrate that for iron(III)-hydrides, hydrogen atom transfer (HAT) is favored over hydrometalation. The oxidation state of iron makes a remarkable difference in the reactivity of the iron-hydride such that ferric FeIII–H is much more reactive in HAT than ferrous FeII–H. Akin to iron(IV)-oxo, exchange-enhanced reactivity (EER) dictates the intrinsic spin HAT reactivity of iron(III)-hydride. However, it is not two-state reactivity (TSR) but single-state reactivity (SSR) that operates in HAT with iron(III)-hydride. The reactivity insights gained herein for alkyl liberation from iron-alkyls may have profound mechanistic implications on the iron-dependent bioorganometallic radical chemistry in radical SAM enzymes.
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