Ligand‐Constraint‐Induced Peroxide Activation for Electrophilic Reactivity

μ-1,2-peroxo-bridged diiron(III) intermediates P are proposed as reactive in various biological oxidation reactions. In sMMO, acts an electrophile, and performs hydrogen atom oxygen transfers to electron-rich substrates. cyanobacterial ADO, however, is postulated react by nucleophilic attack on electrophilic carbon atoms. biomimetic studies, the ability of dimetal complexes Fe, Co, Ni Cu act nucleophiles that effect deformylation aldehydes documented. By performing reactivity theoretical studies end-on μ-1,2-peroxodicobalt(III) complex 1 involving a non-heme ligand system, L1, supported Sn6O6 stannoxane core, we now show peroxo-bridged can also be electrophile. The observed chemistry, which induced constraints provided represents new domain for metal−peroxide reactivity.