Figure 11.
Reaction coordinate for the superoxo intermediate 1a forming the peroxo bridged intermediate 2a (reaction 1, black) and the hydroperoxo bridged intermediate 2b (reaction 2, red) (with electronic energies shown) plotted against the distance between the distal oxygen O(2) and the bridge head C2(3) shown in Figure 4. Electronic energies are quoted relative to the side-on hydroperoxo complex, 1b (i.e. the energy of 1b is 0 kcal/mol). IRCs to the reactant 1a for both of the 2a and 2b led to lower energy structures close to, but not identical to, 1a because the constraint on the positions of the carbon atoms fixed at the crystallographic structure are slightly relaxed along the IRC. The proton transfer in Reaction 2 occurred automatically during the IRC scan from TS2 back to the reactants.