| Calculateda transition state properties, B3LYP+GD3BJ/Def2-TZVPP/SCRF=ethanol | |||||||
|---|---|---|---|---|---|---|---|
| Highest ΔG‡ for HCl catalysed mechanismd | |||||||
| Ar | ΔG‡trans | rds | |||||
| p-NH2 | 6.36 | TS2 | |||||
| p-OMe | 8.48 | TS1≈TS2 | |||||
| p-Me | 10.04 | TS1≈TS2 | |||||
| p-Cl | 12.28 | TS1 | |||||
| p-H | 13.01 | TS1 | |||||
| p-CN | 18.02 | TS2 | |||||
| p-NO2 | 19.85 | TS2 | |||||
| Computed NCI (non-covalent-interaction) isosurfaces | |||||||
| p-NH2 | trans | cis | |||||
| p-NO2 | trans | cis | |||||
| Computed Molecular orbital (HOMO) isosurfaces | |||||||
| p-NH2 | trans | cis | |||||
| p-NO2 | trans | cis | |||||
| Uncatalyzed reaction, TSb | |||||||
| Ar | ΔG‡trans | νi, cm-1 | C-C, Å | C-O, Å | FAIR data DOI | ||
| p-NH2 | 15.01 | 483 | 1.950 | 3.137 | 10.14469/hpc/4102 | ||
| p-OMe | 18.30 | 448 | 1.917 | 2.807 | 10.14469/hpc/4100 | ||
| p-Me | 20.47 | 447 | 1.915 | 2.660 | 10.14469/hpc/4137 | ||
| p-Cl | 18.51 | 447 | 1.914 | 2.576 | 10.14469/hpc/4098 | ||
| p-H | 21.22c | 452 | 1.919 | 2.574 | 10.14469/hpc/4099 | ||
| p-CN | 21.30 | 450 | 1.915 | 2.482 | 10.14469/hpc/4103 | ||
| p-NO2 | 21.34 | 447 | 1.915 | 2.464 | 10.14469/hpc/4101 | ||
| HCl catalyzed reaction, TS1d | |||||||
| Ar | ΔG‡transc | νi, cm-1 | C-C, Å | C-O, Å | Dipole, D | ΔΔG‡cis-transd | |
| p-NH2 | 4.03 | 312 | 2.082 | 2.297 | 17.91 | +8.19 | |
| p-OMe | 8.45 | 440 | 1.978 | 3.218 | 19.83 | +8.05 | |
| p-Me | 9.89 | 412 | 1.928 | 3.164 | 18.49 | +8.59 | |
| p-Cl | 12.28 | 372 | 1.884 | 3.060 | 19.05 | +8.44 | |
| p-H | 13.01 | 375 | 1.890 | 3.069 | 18.65 | +7.03 | |
| p-CN | 17.62 | 279 | 1.810 | 2.871 | 20.08 | +5.80 | |
| p-NO2 | 18.24 | 238 | 1.788 | 2.793 | 18.70 | +7.02 | |
| HCl catalyzed reaction, TS2 | |||||||
| Ar | ΔG‡transc | νi, cm-1 | Dipole, D | ΔΔG‡cis-transe | Trans ΔΔGprod-reactd |
Cis ΔΔGprod-reacte |
|
| p-NH2 | 6.36 | 243 | 10.66 | -0.29 | -0.19 | -5.04 | |
| p-OMe | 8.48 | 270 | 11.39 | +1.11 | -0.67 | -4.87 | |
| p-Me | 10.04 | 208 | 12.16 | +1.64 | -1.27 | -5.20 | |
| p-H | 11.51 | 82 | 12.98 | f | -0.19 | -4.75 | |
| p-Cl | 11.84 | 101 | 12.94 | f | -0.11 | -4.47 | |
| p-CN | 18.02 | 16 | 16.07 | f | +0.17 | -3.94 | |
| p-NO2 | 19.85 | 17 | 16.34 | f | +0.95 | -3.25 | |
| aAll energies in kcal mol-1; DOI for overall collection containing full data, 10.14469/hpc/3943, bCollection for trans stereochemistry 10.14469/hpc/3984, cΔΔG‡ for cis stereochemistry +5.57 kcal/mol. dCollection for trans stereochemistry, 10.14469/hpc/3985, eCollection for cis stereochemistry, 10.14469/hpc/4068, fTS2 is not a stationary point for this substituent. | |||||||