Table 6.
Activation and Reaction energies in kcal/mol for chlorophenoxy radical decomposition to CO and a chlorinated cyclopentadienyl radical. The values for the phenoxyl radical are also reported for reference. Values relative to phenol are given in parentheses. The model chemistries are B3LYP/6-31G(d,p) (I), BHandHLYP/6-31G(d,p) (II), BHandHLYP/aug-cc-pVDZ (III) and QCISD(T)/6-31G(d,p)//BHandHLYP/6-31G(d,p) (IV).
| Compound | I |
II |
III |
IV |
||||
|---|---|---|---|---|---|---|---|---|
| E a | Δ E rxn | E a | Δ E rxn | E a | Δ E rxn | E a | Δ E rxn | |
| Phenoxyl | 56.4 | 29.6 | 62.9 | 29 | 61.6 | 26.4 | 56.4 | 22.9 |
| 2-Chlorophenoxyl | 52.5 (−3.9) | 26.4 (−3.2) | 60.2 (−2.7) | 25.7 (−3.3) | 58.8 (−2.8) | 22.9 (−3.5) | 54.1 (−2.3) | 19.5 (−3.4) |
| 3-Chlorophenoxyl | 56.5 (+0.1) | 26.1 (−3.5) | 63.0 (+0.1) | 25.9 (−3.1) | 62.0 (+0.4) | 23.5 (−2.9) | 56.3 (−0.1) | 18.9 (−4.0) |
| 4-Chlorophenoxyl | 57.6 (+1.2) | 27.4 (−2.2) | 63.6 (+0.7) | 26.9 (−2.1) | 62.6 (+1.0) | 24.6 (−1.8) | 57.4 (+1.0) | 20.2 (−2.7) |
| 2,3-Dichlorophenoxyl | 24.3 (−5.3) | 59.0 (−3.9) | 23.5 (−5.5) | 57.7 (−3.9) | 21.2 (−5.2) | |||
| 2,4-Dichlorophenoxyl | 24.7 (−4.9) | 61.1 (−1.8) | 24.0 (−5.0) | 60.0 (−1.6) | 21.6 (−4.8) | |||
| 2,5-Dichlorophenoxyl | 23.6 (−6.0) | 59.8 (−3.1) | 23.1 (−5.9) | 58.5 (−3.1) | 23.6 (−2.8) | |||
| 2,6-Dichlorophenoxyl | 26.6 −3.0 | 64.0 (+1.1) | 25.4 (−3.6) | 62.6 (+1.0) | 23.0 (−3.4) | |||
| 3,4-Dichlorophenoxyl | 25.0 (−4.6) | 62.0 (−0.9) | 24.4 (−4.6) | 61.3 (−0.3) | 22.6 (−3.8) | |||
| 3,5-Dichlorophenoxyl | 22.8 (−6.8) | 62.4 (−0.5) | 22.9 (−6.1) | 61.5 (−0.1) | 20.7 (−5.7) | |||
| 2,3,4-Trichlorophenoxyl | 22.2 (−7.4) | 57.9 (−5.0) | 21.1 (−7.9) | 57.0 (−4.6) | 19.2 (−7.2) | |||
| 2,3,5-Trichlorophenoxyl | 20.7 (−8.9) | 58.3 (−4.6) | 20.4 (−8.6) | 57.2 (−4.4) | 18.2 (−8.2) | |||
| 2,3,6-Trichlorophenoxyl | 23.9 (−5.7) | 62.7 (−0.2) | 22.6 (−6.4) | 61.5 (−0.1) | 20.4 (−6.0) | |||
| 2,4,5-Trichlorophenoxyl | 22.0 (−7.6) | 59.1 (−3.8) | 21.2 (−7.8) | 58.2 (−3.4) | 19.2 (−7.2) | |||
| 2,4,6-Trichlorophenoxyl | 24.3 (−5.3) | 64.7 (+1.8) | 23.2 (−5.8) | 63.6 (+2.0) | 21.0 (−5.4) | |||
| 3,4,5-Trichlorophenoxyl | 21.3 (−8.3) | 59.7 (−3.2) | 20.7 (−8.3) | 59.2 (−2.4) | 19.2 (−7.2) | |||
| 2,3,4,5-Tetrachlorophenoxyl | 55.4 (−7.5) | 17.3 (−11.7) | 54.7 (−6.9) | 15.8 (−10.6) | ||||
| 2,3,5,6-Tetrachlorophenoxyl | 60.6 (−2.3) | 19.5 (−9.5) | 59.5 (−2.1) | 17.6 (−8.8) | ||||
| 2,3,4,6-Tetrachlorophenoxyl | 60.9 (−2.0) | 19.9 (−9.1) | 60.0 (−1.6) | 18.2 (−8.2) | ||||
| Pentachlorophenoxyl | 57.1 (−5.8) | 16.3 (−12.7) | 56.5 (−5.1) | 15.1 (−11.3) | ||||