Table 7.
Activation and Reaction energies in kcal/mol for bimolecular chlorinated phenoxyl radical-molecular oxygen channels. 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/addition | I |
II |
III |
IV |
||||
|---|---|---|---|---|---|---|---|---|
| E a | Δ E rxn | E a | Δ E rxn | E a | Δ E rxn | E a | Δ E rxn | |
| Ortho-addition | ||||||||
| Phenoxyl | 13.7 | 9.3 | 23.5 | 12.3 | 23.8 | 12.7 | 14.6 | 1.8 |
| 2-Chlorophenoxyl (to C-6) | 14.9 (+1.2) | 11.5 (+2.2) | 24.3 (+0.8) | 13.6 (+1.3) | 24.7 (+0.9) | 14.3 (+1.6) | 15.5 (+0.9) | 3.0 (+1.2) |
| 2-Chlorophenoxyl (to C-2) | 15.7 (+2.0) | 12.5 (+3.2) | 25.8 (+2.3) | 14.9 (+2.6) | 25.9 (+2.1) | 15.2 (+2.5) | 15.2 (+0.6) | 2.9 (+1.1) |
| 3-Chlorophenoxyl (to C-6) | 13.2 (−0.5) | 9.0 (−0.3) | 23.2 (−0.3) | 11.6 (−0.7) | 23.3 (−0.5) | 11.9 (−0.8) | 14.0 (−0.6) | 0.7 (−1.1) |
| 3-Chlorophenoxyl (to C–2) | 13.7 (0.0) | 9.8 (+0.5) | 23.8 (+0.3) | 13.0 (+0.7) | 24.3 (+0.5) | 13.8 (+1.1) | 15.0 (+0.4) | 2.1 (+0.3) |
| 4-Chlorophenoxyl | 14.6 (+0.9) | 11.3 (+2.0) | 24.2 (+0.7) | 13.9 (+1.6) | 24.5 (+0.8) | 14.4 (+1.7) | 15.2 (+0.6) | 3.4 (+1.6) |
| Para-addition | ||||||||
| Phenoxyl | 10.8 | 6.2 | 20.7 | 8.4 | 20.9 | 8.5 | 11.1 | −2 |
| 2-Chlorophenoxyl | 13.8 (+3.0) | 7.9 (+1.7) | 23.1 (+2.4) | 9.8 (+1.4) | 22.9 (+2.0) | 9.9 (+1.4) | 15.8 (+4.7) | −0.5 (+1.5) |
| 3-Chlorophenoxyl | 10.7 (−0.1) | 7.3 (+1.1) | 20.7 (0.0) | 9.4 (+1.0) | 20.8 (−0.1) | 9.6 (+1.1) | 10.7 (−0.4) | −1.9 (+0.1) |
| 4-Chlorophenoxyl | 14.2 (+3.4) | 9.7 (+3.5) | 24.6 (+3.9) | 12.1 (+3.7) | 24.2 (+3.3) | 12.1 (+3.6) | 14.1 (+3.0) | −0.1 (+1.9) |