Manganese and Nickel Complexes as Catalysts for Aromatic Oxidation

Abstract

The development of selective aromatic oxidation catalysts based on non-noble metals has emerged over the last decades, mainly due to the importance of phenol products as intermediates for the generation of pharmaceuticals or functional polymers. In nature, metalloenzymes can perform a wide variety of oxidative processes using molecular oxygen, including arene oxidations, however, the implementation of such enzymes in the chemical industry remains challenging. In this context, chemists have tried to mimic nature and design synthetic non-noble metal catalysts inspired by these enzymes. This introduction chapter aims at providing a general overview on aromatic oxidation reactions catalyzed by metalloenzymes as well as synthetic first-row transition-metal complexes as homogeneous catalysts. The enzymes and complexes discussed in this chapter have been classified on the basis of the transition-metal ion present in their active site, i.e., iron, copper, nickel, and manganese. The main points of discussion focus on enzyme structure and function, catalyst design, mechanism of operation in terms of oxidant activation and substrate oxidation, and substrate scope. At the end of the chapter, the aim and scope of this thesis is outlined.