Table 6.
Class III Substrates of Hperoxo: Correlation Between kobs and BDE
| Substratea | ksat (s-1) | D(R+H-) (kcal/mol)b | -ΔGhydride (R+)s (kcal/mol)c | D(RH) (kcal/mol) |
|---|---|---|---|---|
| CH3CH2CHO | 6.0 ± 0.2 | 224 | 103.8 | 87.5f |
| CH3CHO | 7.6 ± 0.2 | 231.4 | 110.5 | 94.3d |
| CH3NO2 | 0.912 ± 0.002 | - | - | 96.3d |
| HCOONa | 0.71 ± 0.04 | 267e | 142.7 | 96.6d,e |
a
D(R+H-) and D(RH) are given for the bolded C–H bond.
b
Data from (64).
c
Calculated using -ΔGhydride (R+)s = 0.904D(R+H-) – 98.7 kcal/mol from (65). This relationship was originally derived for aromatic molecules in acetonitrile and DMSO, but should provide a good approximation for non-aromatic systems in aqueous solution.
d
Data from (47)
e
These values were originally determined for HCOOH but should approximate that of HCOONa.
f
Data from (66).