Iron(IV) Porphyrin Difluoride Does Not Exist: Implications for DFT Calculations on Heme Protein Reaction Pathways.

DFT (B3LYP as well as a number of common exchange-correlation functionals) predicts a low-spin Fe(IV) ground state for Fe(P)F2 (P = porphyrinato), whereas electrochemical evidence has apparently indicated an Fe(III) porphyrin π-cation radical formulation for such a species. Ab initio CASPT2 calculations favor a high-spin porphyrin π-cation radical as the ground state by a significant energetic margin, thus dramatically overturning the DFT results. In contrast, both DFT and CASPT2 calculations correctly indicate a true Mn(IV) ground state for Mn(P)F2. The remarkable failure of DFT to correctly predict the metal- versus ligand-oxidized nature of Fe(P)F2 may have significant ramifications for the theoretical modeling of heme protein reaction pathways where until now the performance of DFT has raised little concern.