Table 5.
Key parameters of critical structures in cycloadditions of nitroethene (1) to the N-oxides 2a, 2d, and 2h according to B3LYP/6-31G(d) (PCM) calculations
| Solvent | Reaction | Structure | C3–C4 | C5–O1 | ∆l |
μ
D
(D) |
GEDT (e) |
||
|---|---|---|---|---|---|---|---|---|---|
| r (Å) | l | r (Å) | l | ||||||
| Toluene | 1 + 2a | MC | 4.896 | 3.371 | 4.96 | 0.00 | |||
| TS A | 2.356 | 0.451 | 2.009 | 0.615 | 0.16 | 8.50 | 0.12 | ||
| 3a | 1.521 | 1.450 | 6.01 | 0.13 | |||||
| TS B | 2.140 | 0.589 | 2.316 | 0.331 | 0.26 | 12.34 | 0.10 | ||
| 4a | 1.516 | 1.387 | 8.86 | 0.15 | |||||
| 1 + 2d | MC | 4.459 | 4.374 | 2.04 | 0.00 | ||||
| TS A | 2.317 | 0.477 | 2.073 | 0.571 | 0.09 | 5.03 | 0.05 | ||
| 3d | 1.521 | 1.450 | 3.54 | 0.15 | |||||
| TS B | 2.159 | 0.575 | 2.362 | 0.304 | 0.27 | 8.25 | 0.08 | ||
| 4d | 1.515 | 1.393 | 5.68 | 0.17 | |||||
| 1 + 2h | MC | 3.830 | 3.089 | 4.97 | 0.00 | ||||
| TS A | 2.306 | 0.483 | 2.116 | 0.546 | 0.06 | 5.10 | 0.02 | ||
| 3h | 1.520 | 1.455 | 5.98 | 0.18 | |||||
| TS B | 2.174 | 0.564 | 2.370 | 0.304 | 0.26 | 3.86 | 0.05 | ||
| 4h | 1.514 | 1.398 | 4.61 | 0.20 | |||||
| Water | 1 + 2d | MC | 4.330 | 4.420 | 3.24 | 0.00 | |||
| TS A | 2.324 | 0.472 | 2.047 | 0.591 | 0.12 | 5.58 | 0.09 | ||
| 3d | 1.522 | 1.452 | 4.28 | 0.18 | |||||
| TS B | 2.140 | 0.586 | 2.378 | 0.293 | 0.29 | 9.44 | 0.09 | ||
| 4d | 1.514 | 1.393 | 6.52 | 0.19 | |||||