Copper–oxygen adducts: new trends in characterization and properties towards C–H activation

Abstract

This review summarizes the latest discoveries in the field of C–H activation by copper monoxygenases and more particularly by their bioinspired systems. This work first describes the recent background on copper-containing enzymes along with additional interpretations about the nature of the active copper–oxygen intermediates. It then focuses on relevant examples of bioinorganic synthetic copper–oxygen intermediates according to their nuclearity (mono to polynuclear). This includes a detailed description of the spectroscopic features of these adducts as well as their reactivity towards the oxidation of recalcitrant C_sp³–H bonds. The last part is devoted to the significant expansion of heterogeneous catalytic systems based on copper–oxygen cores (i.e. within zeolite frameworks).