Oxidation processes of hydrocarbons in a selective, efficient and environment-friendly manner remains a major challenges.[1-4] The majority of these studies is based on experiment, and computational chemistry plays sometimes an important role, in giving a description of e.g. spectroscopy or TS structures to lead to a deeper understanding. This is in particular true for the influence of the spin state on reactivity.[4] The oxidation reactions on hydrocarbons usually involve high-valent metal-oxo (FeIV=O, MnV=O) or metal-hydroxo (FeIV-OH, NiIII-OH)[5-6] species. Here we explore iron(IV)-oxo complexes and how changes in the ligand sphere influence both the efficiency of the reactions and the pathways taken.[7] Moreover, we break down the reactivity patterns into two complementary building blocks: (i) the reactivity of the iron-oxo unit and coordinating atoms (through model systems as shown in the Figure), and (ii) variations thereof by the real ligand systems. This breakdown brings forward valuable new insights that can be used for the design of new ligands with desired selectivity or improved efficiency.

Inner side of high-valent metal-oxo reactivity

253rd National Meeting (2017)

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