Table 3.
ΔG ≠ for endo and exo structures, ΔΔG ≠ and endo:exo ratio for reactions R1, R2 and R3. Energies are in kcal/mol. ωB97XD/6‐311++G(d) values are taken from Ramirez et al., [26] which also reports the experimental values for endo:exo ratios.
|
|
Endo |
Exo |
ΔΔG≠ |
Ratio |
|---|---|---|---|---|
|
R1 | ||||
|
CAM−B3LYP/6‐31G |
21.81 |
23.23 |
1.42 |
11 : 1 |
|
CAM−B3LYP‐GD3BJ/6‐31G |
17.71 |
19.39 |
1.69 |
17 : 1 |
|
LC‐ωPBE/6‐31G |
22.21 |
24.02 |
1.81 |
21 : 1 |
|
LC‐ωPBE‐GD3BJ/6‐31G |
17.46 |
19.30 |
1.84 |
22 : 1 |
|
ωB97XD/6‐31G |
18.58 |
20.37 |
1.79 |
20 : 1 |
|
SOGGA11X/6‐31G |
20.32 |
21.33 |
1.02 |
5.5 : 1 |
|
M11/6‐31G |
18.68 |
20.42 |
1.74 |
19 : 1 |
|
MN12SX/6‐31G |
17.63 |
18.94 |
1.31 |
9 : 1 |
|
ωB97XD/6‐311++G(d) |
19.4 |
21.1 |
1.7 |
18 : 1 |
|
Experiments |
|
|
|
11 : 1 |
|
R2 | ||||
|---|---|---|---|---|
|
CAM−B3LYP/6‐31G |
20.86 |
22.80 |
1.93 |
26 : 1 |
|
CAM−B3LYP‐GD3BJ/6‐31G |
15.97 |
17.67 |
1.70 |
18 : 1 |
|
LC‐ωPBE/6‐31G |
21.49 |
23.35 |
1.86 |
23 : 1 |
|
LC‐ωPBE‐GD3BJ/6‐31G |
15.45 |
17.45 |
2.00 |
29 : 1 |
|
ωB97XD/6‐31G |
16.39 |
18.64 |
2.26 |
45 : 1 |
|
SOGGA11X/6‐31G |
19.11 |
21.07 |
1.96 |
27 : 1 |
|
M11/6‐31G |
17.10 |
18.80 |
1.69 |
17 : 1 |
|
MN12SX/6‐31G |
13.00 |
13.54 |
0.53 |
31 : 1 |
|
ωB97XD/6‐311++G(d) |
17.4 |
19.5 |
2.1 |
35 : 1 |
|
Experiments |
|
|
|
9.2 : 1 |
|
R3 (R=Me) | ||||
|---|---|---|---|---|
|
CAM−B3LYP/6‐31G |
23.56 |
25.05 |
1.49 |
12 : 1 |
|
CAM−B3LYP‐GD3BJ/6‐31G |
17.41 |
18.54 |
1.12 |
7 : 1 |
|
LC‐ωPBE/6‐31G |
24.34 |
25.77 |
1.44 |
11 : 1 |
|
LC‐ωPBE‐GD3BJ/6‐31G |
16.96 |
19.12 |
2.16 |
39 : 1 |
|
ωB97XD/6‐31G |
17.79 |
18.42 |
0.63 |
3 : 1 |
|
SOGGA11X/6‐31G |
21.83 |
22.95 |
1.13 |
7 : 1 |
|
M11/6‐31G |
18.75 |
20.50 |
1.76 |
19 : 1 |
|
MN12SX/6‐31G |
17.57 |
18.69 |
1.12 |
7 : 1 |
|
ωB97XD/6‐311++G(d) |
21.0 |
21.7 |
0.7 |
3.3 : 1 |
|
R3 (R=Benzyl) | ||||
|---|---|---|---|---|
|
CAM−B3LYP/6‐31G |
24.21 |
25.84 |
1.63 |
16 : 1 |
|
CAM−B3LYP‐GD3BJ/6‐31G |
17.79 |
18.42 |
0.64 |
3 : 1 |
|
LC‐ωPBE/6‐31G |
24.95 |
26.62 |
1.67 |
17 : 1 |
|
LC‐ωPBE‐GD3BJ/6‐31G |
16.45 |
18.73 |
2.28 |
47 : 1 |
|
ωB97XD/6‐31G |
17.89 |
18.75 |
0.86 |
4 : 1 |
|
SOGGA11X/6‐31G |
22.24 |
22.86 |
0.59 |
3 : 1 |
|
M11/6‐31G |
18.10 |
19.60 |
1.50 |
13 : 1 |
|
MN12SX/6‐31G |
17.17 |
19.04 |
1.86 |
23 : 1 |
|
Experiments |
|
|
|
>20 : 1 |