Table 1. Comparison of Barriers and Thermodynamics for O–O Cleavage Using BP86 and B3LYP.
| reactionb | ΔGǂ (ΔEǂ)a | G° (ΔE°)a | ||
|---|---|---|---|---|
|
|
|
|||
| BP86 | B3LYP | BP86 | B3LYP | |
| O–O homolysis of 1 (no PhOH, yielding CuII–O•) | 17.5 (17.6) | 20.2 (20.6) | +8.8 (+9.8) | +10.1 (+10.9) |
| H-bond-assisted O–O cleavage (without PT from PhOH, yielding CuII–O•) | 10.0 (10.9) | 16.4 (17.5) | +4.1 (+7.4) | +5.6 (+8.3) |
| Proton-initiated O–O cleavage (yielding P) | 7.9 (11.7) | 24.3 (25.7) | −12.0 (−6.1) | −5.8 (−2.0) |
| {1} + {PhOH} → {FeIV=O + CuII—OH} + {PhO•} | −7.9 (−5.3) | −9.9 (−7.4) | ||
a
All energies are in kcal/mol, at −80 °C.
b
Braces indicate separately calculated species.