Table 4. Reaction Profiles for the cis-Dihydroxylation of Nitrobenzene and 2-Nitrotoluene According to the Mechanism Passing through a Radical Intermediate Formed in a Direct Attack of HO–FeV=O Species on the Substratea.
| ΔG [kcal mol–1] |
||||
|---|---|---|---|---|
| nitrobenzene |
2-nitrotoluene |
|||
| model 1 | model 2 | model 1 | model 2 | |
| reactant complex | 0.0 | 0.0 | 0.0 | 0.0 |
| TS1 | 7.0 | 2.4 | 0.4 | 2.4 |
| radical intermediate | –5.5 | –7.4 | –6.9 | –9.2 |
| TS2 | –2.4 | –4.6 | –4.3 | –5.6 |
| diol | –42.9 | –47.1 | –47.5 | –48.0 |
a
The Gibbs free energy values were obtained using two different models of the active site (see text for details).