Cobalt Superoxo and Alkylperoxo Complexes Derived from Reaction of Ring-Cleaving Dioxygenase Models with O2

The syntheses and O2 reactivities of active-site models of cobalt-substituted ring-cleaving dioxygenases are presented. The pentacoordinate cobalt­(II)-aminophenolate complex, [Co­(TpMe2)­(tBu2APH)], gives rise to two distinct dioxygen adducts at reduced temperatures. The first is a paramagnetic (S = 1/2) cobalt­(III)-superoxo species that was characterized with spectroscopic and computational techniques. The identity of the second Co/O2 adduct was elucidated by X-ray crystallography, which revealed an unprecedented cobalt­(III)-alkylperoxo structure generated by O2 addition to the metal ion and ligand. These results provide synthetic precedents for proposed intermediates in the catalytic cycles of O2-activating cobalt enzymes.