The most reactive iron and manganese complexes with N-pentadentate ligands for dioxygen activation—synthesis, characteristics, applications

The iron and manganese complexes that activate oxygen atom play multiple role in technologically relevant reactions as well as in biological transformations, in which exist in different redox states. Among them, high-valent oxo intermediate seems to be the most important one. Iron, and/or manganese-based processes have found application in many areas, starting from catalysis and sustainable technologies, through DNA oxidative cleavage, to new substances useful in chemotherapeutic drugs. This review is not only the latest detailed list of uses of homogeneous N-pentadentate iron and manganese catalysts for syntheses of valuable molecules with huge applications in green technologies, but also a kind of "a cookbook", collecting "recipes" for the discussed complexes, in which the sources necessary to obtain a full characterization of the compounds are presented. Following the catalytic activity of metalloenzymes, and taking into account the ubiquity of iron and manganese salts, which in combination with properly designed ligands may show similarity to natural systems, the discussed complexes can find application as new anti-cancer drugs. Also, owing to ability of oxygen atom to exchange in reaction with H(2)O, they can be successfully applied in photodriven reactions of water oxidation, as well as in chemically regenerated fuel cells as a redox catalyst. GRAPHICAL ABSTRACT: [Image: see text]