Table 1. Reaction Free Energies and Barriers of the SuFEx Reaction Showing the Influence of Solvent (H2O), Side Product (HF) and Base (N(CH3)3)a.
| solvent description | ΔG° | (ΔΔG°) | ΔG‡ | (ΔΔG‡) |
|---|---|---|---|---|
| in vacuo | –27 | (0) | 170 | (0) |
| +H2O (implicit) | –41 | (−14) | 157 | (−13) |
| +H2O (explicit) | –32 | (−5) | 165 | (−5) |
| +HF | –2 | (+25) | 175 | (+5) |
| +N(CH3)3 | –60 | (−33) | 143 | (−27) |
| +HF and N(CH3)3 | –33 | (−6) | 143 | (−27) |
a
All energies in kJ/mol at PBE0/def2-TZVPP//PBE/def2-TZVPP. Solvent correction at PBE/def2-TZVPP. Gibbs free energies (ΔG°, ΔG‡) are given with respect to the pre- and post-complexes with the shortest Euclidian distance to the TS (see Figure S2 in the Supporting Information for product structures) and changes w.r.t. the in vacuo value are given in parentheses (ΔΔG°, ΔΔG‡). Electronic energies (ΔE) are listed in the Supporting Information (Table S2) as well.