dioxygen

oxides

hydrogenase

diiron

oxidant

cofactor

iv sup

hydrogenases

ACS Central Science

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.

Heme and Nonheme High-Valent Iron and Manganese Oxo Cores in Biological and Abiological Oxidation Reactions