Skip to main content
. Author manuscript; available in PMC: 2014 Feb 27.
Published in final edited form as: J Am Chem Soc. 2013 Feb 14;135(8):3286–3299. doi: 10.1021/ja400183g

Figure 9.

Figure 9

(A) S = 1/2, 3/2, and 5/2 (LS, IS, and HS) PES (ΔH/ΔG at 253 K, with solvent correction, in kcal/mol) for the reaction of the [(TMC)FeIII–OOH]2+ complex with xanthene. The transition states energies were calculated as the energy difference between transition state and reactant components calculated in one box. The products energies were calculated as the energy difference between product and reactant components calculated in separate boxes to prevent electron transfer from product radical to [(TMC)FeIV=O]2+. (B) S = 5/2 transition state structure for the direct H-atom abstraction reaction between the HS [(TMC)FeIII–OOH]2+ complex and xanthene. Fe atom is in green, N atoms are in blue, C atoms are in black, O atoms are in red, H atom is in white. Only important H atoms are shown, others are omitted for clarity. Note that the axial ligand, modeled as acetonitrile for the reason mentioned in section 2.4, is not coordinated in the TS (4.39 Å) on the HS PES.