Metal–Oxo Complexes

Dear Colleagues,

Nature utilizes metalloenzymes for important biotransformations, ranging from biosynthesis to biodegradation of compounds. Often, molecular oxygen is used on a catalytic center and converted into a high-valent metal–oxo species. For instance, the active species of typical drug metabolizing enzymes in the human liver, namely the cytochromes P450, is an iron(IV)–oxo heme species called Compound I. However, the ligand system of these metal–oxo species strongly affects the reactivity and chemical properties so that heme and non-heme metal–oxo species have different properties and functionalities. Due to the short lifetime of these metal–oxo complexes, they are difficult to trap and characterize experimentally but in recent year’s advances through the use of biomimetic and synthetic model complexes alongside computational modelling has been made. These combinations of experimental and computational studies on synthetic models and enzymes has given insight into the reactivity patterns of these systems, as well as the properties and structure that determine the reactivity patterns. Thus, metal–oxo species are efficient oxidants that react with substrates through oxygen atom transfer, dehydrogenation, but also may be intermediates in water oxidation processes in general catalysis. Therefore, they are important intermediates in catalysis and biochemistry and understanding their intrinsic chemical features enables future design of novel catalysts.

Prof. Dr. Sam P. de Visser
Guest Editor

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