| Calculated(a) transition state properties, B3LYP+GD3BJ/Def2-TZVPP/SCRF=ethanol |
|---|
| 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 |
| 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 |
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.