Ligand‐Constraint‐Induced Peroxide Activation for Electrophilic Reactivity

μ‐1,2‐peroxo‐bridged diiron(III) intermediates P are proposed as reactive intermediates in various biological oxidation reactions. In sMMO, P acts as an electrophile, and performs hydrogen atom and oxygen atom transfers to electron‐rich substrates. In cyanobacterial ADO, however, P is postulated to react by nucleophilic attack on electrophilic carbon atoms. In biomimetic studies, the ability of μ‐1,2‐peroxo‐bridged dimetal complexes of Fe, Co, Ni and Cu to act as nucleophiles that effect deformylation of aldehydes is documented. By performing reactivity and theoretical studies on an end‐on μ‐1,2‐peroxodicobalt(III) complex 1 involving a non‐heme ligand system, L1, supported on a Sn(6)O(6) stannoxane core, we now show that a peroxo‐bridged dimetal complex can also be a reactive electrophile. The observed electrophilic chemistry, which is induced by the constraints provided by the Sn(6)O(6) core, represents a new domain for metal−peroxide reactivity.