Figure 11.

Diagram depicting the DFT-calculated transformation from a superoxo species to Int1 as described by transfer of a proton and an electron from the substrate to the superoxo ligand (proton-coupled electron transfer, PCET). The water molecule indicated is crystallographic WatC. Solid and dashed lines indicate the lowest spin septet and quintet states, respectively, for each conformation. Atoms highlighted in red are involved in hydrogen bonding interactions that affect the transfer. Energies on the left and right frame refer to the energies of the S = 3 states.