Reductive cleavage of O-O bond is of extreme importance for oxygen activation in biochemical systems. In cytochrome p450 compound 0, an (Fe(III)-OOH) reacts with a proton to generate P.Fe(IV)=O and H2O. This poster will provide evidence that Cu undergoes an alternative mechanism. Specifically, we have identified a key model system [LCuII-(OOR)]+2 in which addition of acid results in homolytic O-O bond rupture based on spectroscopy and product analysis. Computational studies indicate that this process is driven by protonation of the proximal peroxo oxygen, which avoids generation of the highly basic Cu(III)=O group. This work represents the first example of a controlled O-O bond cleavage and consequently serves as a platform for continued studies which will be discussed.

Proton induced cleavage of O-O bond in mononuclear cupper complexes

ACS Spring Meeting 2021

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