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 s MMO, 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 nonheme 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.