Inspired by oxidation enzymes such as P450 and TauD, several groups have based their research on the iron−oxo moiety in the field of alkanes partial oxidation. Still, the controlled cleavage and oxidation of the aliphatic C−H bond remains a prized goal in chemistry. Among all oxidation processes, the selective oxidation of methane into methanol is certainly one of the most challenging task. Based on DFT calculations and molecular orbital analysis, we will analyse the role of the ligand field and discuss the importance of the spin state of iron. Based on this analysis, we will then see why iron is so important in oxidation and show that Cobalt could be also a good candidate.1 Then, we will present a computational methodology to predict the comparative reactivity of iron−oxo complexes for this process from linear relations based on the sole electronic structure of the reactant state. The efficient correlation of the C−H activation barrier to a simple but intuitive molecular orbital descriptor enables the design of ligands that permit low barrier C−H abstraction steps and the fast screening of novel potential complexes.2 The activation of the catalyst by a multidentate effect is also evidenced. We anticipate this study to improve the rational design of hydrocarbon oxidation catalysts. 1- C. Michel, E.J. Baerends, Inorg. Chem. 2009, 48, 3628 2- Prokopis C. Andrikopoulos, Carine Michel, Sandra Chouzier, Philippe Sautet , ACS Catalysis, 2015, 2490

Iron-oxo catalysts for CH bond cleavage: Insights from modeling

251st National Meeting (2016)

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