Status of Reactive Non-Heme Metal–Oxygen Intermediates in Chemical and Enzymatic Reactions

• Published in: Journal of the American Chemical Society Vol. 136; no. 40; pp. 13942 - 13958
• Main Authors: Ray, Kallol, Pfaff, Florian Felix, Wang, Bin, Nam, Wonwoo
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08.10.2014
• Subjects: Biomimetics; Enzymes - metabolism; Metals - chemistry; Metals - metabolism; Oxygen - chemistry; Oxygen - metabolism
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja507807v

Selective functionalization of unactivated C–H bonds, water oxidation, and dioxygen reduction are extremely important reactions in the context of finding energy carriers and conversion processes that are alternatives to the current fossil-based oil for energy. A range of metalloenzymes achieve these challenging tasks in biology by using cheap and abundant transition metals, such as iron, copper, and manganese. High-valent metal–oxo and metal–dioxygen (superoxo, peroxo, and hydroperoxo) cores act as active intermediates in many of these processes. The generation of well-described model compounds can provide vital insights into the mechanisms of such enzymatic reactions. This perspective provides a focused rather than comprehensive review of the recent advances in the chemistry of biomimetic high-valent metal–oxo and metal–dioxygen complexes, which can be related to our understanding of the biological systems.