Dioxygen Activation by Copper-Bleomycin: Theoretical Considerations

Density functional theory (DFT) calculations are employed to calculate probable reaction intermediates in dioxygen activation by bleomycin-ligated copper - Cu(I)-dioxygen, Cu(I)-superoxo and Cu(II)-hydroperoxo. The electronic structures of these intermediates are discussed with emphasis on their electromerism. Importantly, unlike in dioxygen activation by iron-bleomycin, formation of these reactive intermediates requires that some of the copper-bleomycin bonds be broken. (doi: 10.5562/cca1793)