O2 Activation and selective phenolate ortho hydroxylation by an unsymmetric dicopper -η1:η1-peroxido complex

A novel unsymmetric dicopper complex gives rise to an asymmetric [Cu2(O2)(m-XYLN3N4)]2+ species (1O2), where the O2 molecule binds as a peroxide in a -η1:η1-O2 mode. 1O2 exhibits hitherto reactivity patterns so far not observed for symmetric analogues. It is basically nonreactive in oxygen atom transfer reactions, but it contains an available coordination site that selectively binds and mediates phenolate ortho-hydroxylation; thus constituting an exquisitely selective and conceptually alternative tyrosinase functional model.