In Silico Screening of Iron-Oxo Catalysts for CH Bond Cleavage

Abstract

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. We present here 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. 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.