Macroheterocyclic μ-Nitrido- and μ-Carbido Dimeric Iron and Ruthenium Complexes as a Molecular Platform for Modeling Oxidative Enzymes (A Review)

Recent scientific publications demonstrate a new approach to modeling catalysts that mimic heme-containing enzymes. It involves the use of μ-oxo, μ-nitrido, and μ-carbido dimeric transition metal complexes as promising mimetics. The high catalytic activity of μ-nitrido dimeric iron(III,IV) complexes with porphyrin-type macrocycles, mediated by the formation of high-valence oxo forms similar to the redox site of oxidative enzymes, stimulates interest in such compounds. In this review, special attention is focused on studies aimed at scrutinizing the chemical principles of the formation of different types of highly oxidized oxo forms of μ-nitrido and μ-carbido dimeric iron(IV) and ruthenium(IV) complexes and modulation of their reactivity. Here data on the spectral, coordination, and redox properties of μ-nitrido and μ-carbido dimeric iron(IV) and ruthenium(IV) complexes are summarized, their comparative analysis is performed, and the possibility of using these compounds as a molecular platform for modeling oxidative enzymes is demonstrated. It is noted that the bimetallic structure is flexible and has significant potential for further development and fine tuning of properties through the inclusion of various ligands, metals, and bridging groups in the structure.