Halogen Transfer to Carbon Radicals by High-Valent Iron Chloride and Iron Fluoride Corroles.

High-valent iron halide corroles were examined to determine their reactivity with carbon radicals and their ability to undergo radical rebound-like processes. Beginning with Fe(Cl)(ttppc) () (ttppc = 5,10,15-tris(2,4,6-triphenylphenyl)corrolato), the new iron corroles Fe(OTf)(ttppc) (), Fe(OTf)(ttppc)(AgOTf) (), and Fe(F)(ttppc) () were synthesized. Complexes and are the first iron triflate and iron fluoride corroles to be structurally characterized by single crystal X-ray diffraction. The structure of reveals an Ag-pyrrole (η-π) interaction. The Fe(Cl)(ttppc) and Fe(F)(ttppc) complexes undergo halogen transfer to triarylmethyl radicals, and kinetic analysis of the reaction between (-OMe-CH)C• and gave = 1.34(3) × 10 M s at 23 °C and 2.2(2) M s at -60 °C, Δ = +9.8(3) kcal mol, and Δ = -14(1) cal mol K through an Eyring analysis. Complex is significantly more reactive, giving = 1.16(6) × 10 M s at 23 °C. The data point to a concerted mechanism and show the trend X = F > Cl > OH for Fe(X)(ttppc). This study provides mechanistic insights into halogen rebound for an iron porphyrinoid complex.