The transfer of OH• from metal-hydroxo species to carbon radicals (R•) to give hydroxylated products (ROH) is a fundamental process in metal-mediated heme and nonheme C-H bond oxidations. This step, often referred to as the hydroxyl "rebound" step, is typically very fast, making direct study of this process challenging if not impossible. In this report, we describe the reactions of the synthetic models M(OH)(ttppc) (M = Fe (1), Mn (3); ttppc = 5,10,4,6

The corrole ligand serves as a versatile tri-anionic, macrocyclic platform on which to model biological catalytic systems, as well as to effect mechanistically challenging chemical transformations. Herein we describe the synthesis, structure, and characterization of an isomerically pure corrole ligand, selectively mono-brominated at the β-carbon position adjacent to the corrole C-C bond (2-C) and produced in relatively high yields, as well as its iron chloride complex. Analysis of the iron metalated complex by cyclic voltammetry shows that the bromine being present on the ligand resulted in anodic shifts of +93 and +63 mV for first oxidation and first reduction of the complex respectively. The Mössbauer spectrum of the iron metalated complex shows negligible change relative to the non-brominated analog, indicating the presence of the halide substituent predominantly effects the orbitals of the ligand rather than the metal.