Dioxygen-Derived Nonheme Mononuclear FeIII(OH) Complex and Its Reactivity with Carbon Radicals

A new tetradentate, monoanionic, mixed N/O donor ligand (BNPAPh2O–) with second coordination sphere H-bonding groups has been synthesized for stabilization of a terminal FeIII(OH) complex. The complex FeII(BNPAPh2O)­(OTf) (1) reacts with O2 to give a mononuclear terminal FeIII(OH) complex, FeIII(OH)­(BNPAPh2O)­(OTf) (2), both of which were characterized by X-ray diffraction, electrospray ionization mass spectrometry, UV–vis, 1H and 19F nuclear magnetic resonance, 57Fe Mössbauer, and electron paramagnetic resonance spectroscopies. Treatment of 2 with carbon radicals (Ar3C·) gives Ar3COH and the FeII complex 1, in direct analogy with the elusive radical “rebound” process proposed for nonheme iron enzymes.