Table 2. M06-2X/6-311+G(d,p) thermodynamic and kinetic parameters (ΔE, ΔH, ΔG, in kcal mol−1 and ΔS, in cal mol−1 K−1), of the studied HDA reactions.
| ΔE | ΔG | ΔH | ΔS | −TΔS | Populations | |
|---|---|---|---|---|---|---|
| 1 + 2a | ||||||
| TS1-on | 0.25 | 18.55 | 1.16 (6.25%) | −58.33 | 17.39 (93.75%) | 99.99 |
| TS1-ox | 7.31 | 24.73 | 8.02 (32.43%) | −56.03 | 16.70 (67.57%) | 0.01 |
| TS1-mn | 9.92 | 27.54 | 10.72 (38.92%) | −56.43 | 16.82 (61.08%) | — |
| TS1-mx | 10.99 | 29.15 | 11.71 (40.17%) | −58.49 | 17.44 (59.83%) | — |
| CA1-on | −48.53 | −27.21 | −44.80 | −59.02 | 17.60 | — |
| CA1-ox | −54.84 | −33.36 | −50.86 | −58.69 | 17.50 | — |
| CA1-mn | −52.50 | −30.36 | −48.61 | −61.23 | 18.26 | — |
| CA1-mx | −48.79 | −27.43 | −44.83 | −58.37 | 17.40 | — |
| 1 + 2b | ||||||
| TS2-on | 5.55 | 18.30 | 9.91 (54.15%) | −43.44 | 8.39 (45.85%) | 17.35 |
| TS2-ox | 9.75 | 20.86 | 14.07 (67.45%) | −42.83 | 6.79 (32.55%) | 0.29 |
| TS2-mn | 4.29 | 17.28 | 8.70 (50.35%) | −44.52 | 8.58 (49.65%) | 79.59 |
| TS2-mx | 7.20 | 19.39 | 11.56 (59.62%) | −42.99 | 7.84 (40.38%) | 2.77 |
| CA2-on | −46.87 | −31.95 | −39.72 | −45.19 | 7.77 | — |
| CA2-ox | −47.46 | 32.69 | −40.25 | −40.68 | 7.56 | — |
| CA2-mn | −45.97 | −30.58 | −38.73 | −45.73 | 8.15 | — |
| CA2-mx | −50.67 | −35.67 | −43.28 | −43.63 | 7.61 | — |