Acid/base triggered interconversion of μ-η(2):η(2)-peroxido and bis(μ-oxido) dicopper intermediates capped by proton-responsive ligands

CuII2(μ-η(2):η(2)-peroxido) and CuIII2(μ-oxido)(2) cores represent key intermediates in copper/dioxygen chemistry, and they are mechanistically important for biological hydroxylation and oxidation reactions mediated by dinuclear (type III) copper metalloenzymes. While the exact nature of the active species in different enzymes is still under debate, shifting equilibria between Cu(x)/O(2) species is increasingly recognized as a means of switching between distinct reactivity patterns of these intermediates. Herein we report comprehensive spectroscopic, crystallographic and computational analysis of a family of synthetic CuII2(μ-η(2):η(2)-peroxido) and CuIII2(μ-oxido)(2) dicopper complexes with a bis(oxazoline) (BOX) capping ligand. In particular, we demonstrate that a reversible peroxido/bis(μ-oxido) interconversion of the [Cu(2)O(2)] core can be triggered by peripheral (de)protonation events on the ligand backbone. As the copper ions in the enzymes are typically supported by histidine imidazoles that offer a backside N atom amenable to potential (de)protonation, it is well conceivable that the shifting of equilibria between the [Cu(2)O(2)] species in response to changes in local pH is biologically relevant.