aoc6549-sup-0001-Supp-Infor-2021-11-11.docxWord 2007 document , 1 MB

Table S1. The calculated values of electronic energy ∆E, zero-point energy correction ∆ZPE, relative enthalpy ∆H, relative entropy ∆S, Gibb’s free energy ∆Ggas, Gibb’s free energy in solution dichloromethane, ∆Gsol, (298K) for the overall catalytic cycle of iron-catalyzed mechanism to obtain the product P. (The unit of relative entropy ∆S is Cal/mol-K and all other energy units are kcal/mol. The sum of the energies of 1 is set as the zero of energy.)

Figure S1. Fully optimized structures of the triplet and quintuplet of 1, the precatalyst CA, THF, TMP, TMPH, BF3I-, and 8. (Color scheme: C, cyan; N, blue; H, white; O, red; Fe, ochre; I, orange; F, pink; B, black. Distances are given in Å.)

Figure S2. Fully optimized structures of the product (R)-P, the intermediates (R)-5, (R)-6, (R)-7 and the transition state (R)-TS2. (Color scheme: C, cyan; N, blue; H, white; O, red; B, black; F, pink; Fe, ochre; Br, purple. Distances are given in Å.)

Figure S3. Fully optimized structures of the molecule H2O, H3O+, I2, I3-. (Color scheme: H, white; O, red; I, orange. Distances are given in Å.)

Figure S4. Energy profiles ΔE in the gas phase for the whole catalytic cycles to obtain (S)-P (black solid line) and (R)-P (red dashed line), respectively. (The unit of energies is in kcal/mol).

Figure S5. Energy profiles ΔGgas, Gibbs free energies in the gas phase for the whole catalytic cycles to obtain (S)-P (black solid line) and (R)-P (red dashed line), respectively. (The unit of energies is in kcal/mol).

Figure S6. Energy profiles ΔGsol for the whole catalytic cycle when starting from [Fe(Cp)(CO)2(THF)]+, CA. It can be seen that the catalytic cycle is not possible, which is not consistent with the experimental results, so CA is only the pre-catalyst and the catalytic cycle should start from the catalyst 1.