Cleavage and formation of the O–O bond in dioxygen is among the most important metal‐dependent processes in Nature. The former process has been mimicked structurally and functionaly with a number of biomimetic iron complexes. The reverse process, namely the dioxygen bond formation, however, appears unfavorable with iron. Over the years many attempts have been made to oxidize water on a mononuclear iron center through reactions with peroxide. In this work we present a computational study focused on the mechanism of dioxygen formation on two mononuclear non‐heme iron(IV)‐oxo species upon addition of peracid (m‐chloroperbenzoic acid, m CPBA). A range of test reactions and sequences are analyzed with thermochemical cycles with respect to the thermodynamic and kinetic feasibility of product formation. The work shows that iron‐borne O–O bond formation through peracid attack at Fe^IVO indeed is feasible through two competing pathways. These are initiated by homolytic inner‐sphere splitting of the RC(O)OO‐H and the RC(O)O‐OH bond in the peracid, respectively.

中文翻译：

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单核非血红素铁中心O-O键形成的计算研究

双氧中O–O键的裂解和形成是自然界中最重要的金属依赖性过程之一。前一种方法已在结构和功能上与许多仿生铁配合物进行了模仿。然而，相反的过程，即双氧键的形成，似乎对铁不利。多年来，已经进行了许多尝试通过与过氧化物的反应来氧化单核铁中心上的水。在这项工作中，我们提出一个计算研究集中于分子氧形成的机理在两个单核非血红素铁（IV）在加入过酸（的氧代物种米氯过苯甲酸，米CPBA）。关于产物形成的热力学和动力学可行性，通过热化学循环分析了一系列测试反应和序列。这项工作表明，通过Fe ^IV O的过酸攻击形成铁基的O-O键确实可以通过两种竞争途径来实现。这些是通过过酸中的RC（O）OO-H和RC（O）O-OH键的均相内球分裂而引发的。