Table 1. Experimental Rate Constantsa and Calculated Reaction Barriers and Rate Constantsb.
| method Ac |
method Bd |
||||
|---|---|---|---|---|---|
| dipolarophile | log(kexp × 109) | ΔGA‡ (kcal/mol) | log(kcal × 109) | ΔGB‡ (kcal/mol) | log(kcal × 109) |
| R1e | 7.06 | 23.1 | 4.85 | 18.3 | 8.37 |
| R2e | 6.00 | 25.6 | 3.02 | 20.8 | 6.54 |
| R3e | 5.41 | 24.3 | 3.97 | 19.6 | 7.42 |
| R4e | 4.40 | 29.6 | 0.09 | 23.7 | 4.41 |
| R5 | 4.29 | 30.0 | –0.21 | 23.9 | 4.27 |
| R6e | 2.38 | 32.5 | –2.04 | 26.4 | 2.43 |
| R7 | 1.95 | 32.9 | –2.33 | 26.7 | 2.21 |
| R8 | 1.60 | 32.3 | –1.90 | 27.8 | 1.41 |
| R9 | 1.38 | 33.8 | –3.00 | 28.4 | 0.97 |
| R10 | 1.18 | 33.3 | –2.63 | 27.6 | 1.55 |
| R11 | 0.52 | 35.0 | –3.88 | 28.9 | 0.60 |
| R12 | 1.43 | 33.4 | –2.70 | 27.9 | 1.33 |
| R13 | 1.46 | 33.5 | –2.78 | 27.7 | 1.48 |
| R14 | 1.53 | 32.5 | –2.04 | 26.3 | 2.51 |
| R15 | 1.60 | 33.3 | –2.63 | 27.0 | 1.99 |
| R16 | 1.86 | 33.4 | –2.70 | 27.3 | 1.77 |
| R17 | 2.03 | 32.7 | –2.19 | 28.0 | 1.26 |
| R18 | 2.92 | 31.7 | –1.46 | 25.9 | 2.80 |
| R19 | 2.99 | 31.5 | –1.31 | 26.4 | 2.43 |
| R20 | 3.02 | 31.5 | –1.31 | 26.6 | 2.29 |
| R21 | 3.40 | 31.3 | –1.16 | 25.6 | 3.02 |
a
For different dipolarophiles, the corresponding cycloaddition was performed in a particular solvent (carbon tetrachloride or benzene) at 25 °C.30
b
For different dipolarophiles, the calculated reaction barriers and rate constants are values in a specific solvent (carbon tetrachloride or benzene), which was chosen according to what was used in the experiment.30
c
ωB97X-D/aug-cc-pVTZ-CPCM(solvent)//ωB97X-D/6-31+G(d,p)-CPCM(solvent).
d
B2PLYP-D3/aug-cc-pVTZ-CPCM(solvent)//ωB97X-D/6-31+G(d,p)-CPCM(solvent).
e
In the experimental study, the reaction solvent was benzene for these dipolarophiles and carbon tetrachloride for the other dipolarophiles.30