Department of Chemistry, University of Minnesota, Twin Cities, 207 Pleasant Street SE, Minneapolis, MN, 55455, USA.
Angew Chem Int Ed Engl. 2020 May 4;59(19):7332-7349. doi: 10.1002/anie.201906551. Epub 2020 Mar 2.
Nonheme iron enzymes generate powerful and versatile oxidants that perform a wide range of oxidation reactions, including the functionalization of inert C-H bonds, which is a major challenge for chemists. The oxidative abilities of these enzymes have inspired bioinorganic chemists to design synthetic models to mimic their ability to perform some of the most difficult oxidation reactions and study the mechanisms of such transformations. Iron-oxygen intermediates like iron(III)-hydroperoxo and high-valent iron-oxo species have been trapped and identified in investigations of these bio-inspired catalytic systems, with the latter proposed to be the active oxidant for most of these systems. In this Review, we highlight the recent spectroscopic and mechanistic advances that have shed light on the various pathways that can be accessed by bio-inspired nonheme iron systems to form the high-valent iron-oxo intermediates.
非血红素铁酶产生强大且多功能的氧化剂，可进行广泛的氧化反应，包括惰性 C-H 键的功能化，这对化学家来说是一个主要挑战。这些酶的氧化能力启发了生物无机化学家设计合成模型来模拟它们进行一些最困难的氧化反应的能力，并研究这些转化的机制。在对这些受生物启发的催化体系的研究中，已经捕获并鉴定了铁-氧中间体，如铁（III）-过氧氢和高价铁-氧物种，后者被提议为大多数这些体系的活性氧化剂。在这篇综述中，我们重点介绍了最近的光谱和机理进展，这些进展揭示了受生物启发的非血红素铁体系形成高价铁-氧中间体的各种途径。
