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J Am Chem Soc. 2014 Oct 8;136(40):13942-58. doi: 10.1021/ja507807v. Epub 2014 Sep 29.

Status of reactive non-heme metal-oxygen intermediates in chemical and enzymatic reactions.

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Department of Chemistry, Humboldt-Universit├Ąt zu Berlin , 12489 Berlin, Germany.


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.

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