Copper Peroxide Bioinorganic Chemistry: From Metalloenzymes to Bioinspired Synthetic Systems

During the last few decades, copper-dioxygen chemistry has emerged as a new and very active field of (bio)inorganic relevance. Highlighted herein are the major findings, including the principles of dioxygen activation in metal-containing proteins along with characterization and reactivity of natural copper-peroxo systems which are derived from reaction of molecular oxygen with copper(I) active-site centers. Inspired by the varied array of copper proteins-enzymes which have been characterized, synthetic bioinorganic researchers have developed model systems which are amenable to facilitating the electron-transfer and atom-transfer chemistry which pervades dioxygen binding to copper complexes found in various oxidation states (+1 to +3). These studies have provided for new coordination chemistry of fundamental importance. In addition, significant contributions concerning the identity of biological or chemical reactive intermediates and insights into copper enzyme reaction mechanisms have been made. Taking advantage of this rich redox chemistry, synthetic methods combining copper and O2 (or H2O2) have been explored by organic/inorganic chemists, seeking to employ this earth abundant element to replace routes now usually carried out with precious (expensive/non-benign) metals, developing green, sustainable and selective oxidative processes. Keywords: bioinspired systems; biosynthesis; copper-metalloproteins; dioxygen-reduction; organic catalysis; redox-chemistry