Non-heme oxoiron(V) intermediates in chemo-, regio- and stereoselective oxidation of organic substrates

In the last two decades, a number of synthetic iron-based biomimetic catalyst systems for the selective oxidation of organic compounds, such as epoxidations of alkenes and C-H oxidations of alkanes and arenes, have been reported and extensively investigated. In some cases, the mechanisms of their catalytic action have been hypothesized, and the nature of their catalytically active, oxygen-transferring species, has been established. This review is dedicated to the synthetic non-heme perferryl intermediates, formal analogs of Compound I in the catalytic cycle of cytochrome P450. The discovery of perferryl species, their structure and spectroscopic properties, as well as the effect of oxidant nature, ligand structure, and additives on their reactivity and selectivity are discussed. (C) 2019 Elsevier B.V. All rights reserved.