Utilization of O₂ as an abundant and environmentally benign oxidant is of great interest in the design of bioinspired synthetic catalytic oxidation systems. Metalloenzymes activate O₂ by employing earth-abundant metals and exhibit diverse reactivities in oxidation reactions, including epoxidation of olefins, functionalization of alkane C–H bonds, arene hydroxylation, and syn-dihydroxylation of arenes. Metal–oxo species are proposed as reactive intermediates in these reactions. A number of biomimetic metal–oxo complexes have been synthesized in recent years by activating O₂ or using artificial oxidants at iron and manganese centers supported on heme or nonheme-type ligand environments. Detailed reactivity studies together with spectroscopy and theory have helped us understand how the reactivities of these metal–oxygen intermediates are controlled by the electronic and steric properties of the metal centers. These studies have provided important insights into biological reactions, which have contributed to the design of biologically inspired oxidation catalysts containing earth-abundant metals like iron and manganese. In this Outlook article, we survey a few examples of these advances with particular emphasis in each case on the interplay of catalyst design and our understanding of metalloenzyme structure and function.

中文翻译：

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生物和生物氧化反应中的血红素和非血红素高价铁锰锰芯

在生物启发的合成催化氧化系统的设计中，O ₂作为一种丰富且对环境无害的氧化剂的使用引起了人们极大的兴趣。金属酶通过使用富含地球的金属来活化O ₂，并在氧化反应中表现出不同的反应性，包括烯烃的环氧化，烷烃CH键的官能化，芳烃羟基化和芳烃的顺二羟基化。在这些反应中，金属-氧物种被提议为反应性中间体。近年来，通过活化O ₂合成了许多仿生金属-氧配合物或在血红素或非血红素型配体环境下在铁和锰中心使用人工氧化剂。详细的反应性研究以及光谱学和理论知识帮助我们了解了这些金属-氧中间体的反应性如何由金属中心的电子和空间位阻所控制。这些研究为生物反应提供了重要的见识，从而有助于设计出含有铁和锰等地球上富足金属的生物启发性氧化催化剂。在本《展望》文章中，我们调查了这些进展的一些示例，其中每种情况都特别强调了催化剂设计的相互作用以及我们对金属酶结构和功能的理解。