Active sites and mechanisms of bioinspired oxidation with H2O2, catalyzed by non-heme Fe and related Mn complexes

In the last two decades, considerable efforts were invested in the search for synthetic iron and manganese catalysts with nonporphyrinic ligands, mimicking metalloenzymes in the oxygenation at C-H and C=C bonds of organic molecules. In many cases, the detailed knowledge of intimate reaction mechanisms and of the nature of active sites was critical for the rational design of biomimetic catalysts with predictable reactivities. This review discusses the up-to-date mechanistic landscape of non-heme iron and manganese catalyzed oxidations of olefinic groups and aliphatic C-H groups with H2O2. (C) 2014 Published by Elsevier B.V.