Formation of an end-on ferric peroxo intermediate upon one-electron reduction of a ferric superoxo heme.

摘要: The low-spin end-on ferric peroxo heme intermediate has been proposed as an alternative reactive involved in the catalytic cycles of enzymes such nitric oxide synthase and cytochrome P450. This transient never captured using synthetic models. We demonstrate herein our success solution preparation derived from a model, which features both group hanging over porphyrin macrocycle covalently appended axial imidazole ligand, through one-electron reduction its superoxo precursor. obtained was further transformed into corresponding hydroperoxo species upon protonation. model compound provides convenient system for sequential important biologically relevant superoxo/peroxo/hydroperoxo intermediates oxygenation/one-electron reduction/protonation process similar to mechanisms used by enzyme systems.