Molecular Iron-Based Oxidants and Their Stoichiometric Reactions

Molecular iron-based oxidants can oxidize organic substrates under relatively mild conditions, sometimes even in water. If these reactions can be converted to catalytic protocols, they hold great promise for the development of greener methods for this particularly messy class of reaction. For application in organic synthesis, the biggest question is: How selective can the reactions be? The supporting ligands in these compounds are crucial for tuning the electronic structure of a catalytically competent iron-based oxidant and its selectivity in terms of the production of a single, even enantiopure, product. A thorough understanding of the stoichiometric generation of molecular iron-based oxidants and their subsequent reactivity is an important step for the development of new iron-based catalysts. Ideally, and in analogy to many of nature’s iron-based enzymes, their regeneration under catalytic conditions could involve the activation of dioxygen from air. This chapter will focus on the stoichiometric reactions of iron compounds with potential oxidizing agents including O2, peroxides, oxygen-atom donor reagents, and even water, to form iron-based oxidizing species and the reactions of these usually very transient species with oxidizable substrates. This chapter might be especially inspiring for researchers in the field of iron catalyst design.