Computational and Experimental Insights into a Ferric Cumylperoxido Species Stabilized in a Bispidine Scaffold

Iron‐containing alkylperoxido species are mostly unstable, although these are important reactive intermediates found in metalloenzymes. Noncovalent forces in enzymatic systems contribute to their stability and reactivity. Different mechanistic approaches such as OO bond cleavage and FeO bond cleavage are established pathways of their reactivity. However, with a thorough computational study combined with experiments, we have discovered a different approach wherein we report a putative superoxido species orchestrating the unique mechanism. Herein, we discuss the generation and reactivity of an iron(III)‐cumylperoxido intermediate towards sulfoxidation and aldehyde deformylation, supported and corroborated by an in‐depth computational analysis.