Table 12.
ROO•/ROOH | solvent | E∘(ROO•/−) | pKa(ROOH) | E∘ (V vs H2) | BDFE |
---|---|---|---|---|---|
MeOOH | gas | -- | -- | 1.346 | 79.6328 |
MeOOH | H2O | 0.94329 | 11.5330 | 1.62 | 90.2 |
EtOOH | gas | -- | -- | 1.216 | 76.6328 |
EtOOH | H2O | 0.91329 | 11.8330 | 1.61 | 89.9 |
iPrOOH | H2O | 0.81329 | 12.1330 | 1.53 | 88.0 |
tBuOOH | gas | -- | -- | 1.194 | 76.1328 |
tBuOOH | H2O | 0.71329 | 12.8330 | 1.47 | 86.6 |
trans-HC(O)OOH | gas | -- | -- | 1.658 | 86.8331 |
cis-HC(O)OOH | 1.801 | 90.1331 | |||
CH3C(O)OOH | gas | -- | -- | 1.463 | 82.3 |
CH3C(O)OOH | H2O | 1.14b | 8.2330 | 1.63 | 90.3 |
ROOH + H2(g) → ROH + H2O | solvent | E∘(V vs H2) | −ΔG∘/nc | ||
| |||||
MeOH/MeOOH | H2O | 1.70332 | 92.0 | ||
tBuOH/tBuOOH | H2O | 1.68332 | 91.5 | ||
HC(O)OH/HC(O)OOH | H2O | 1.82332 | 94.8 | ||
CH3C(O)OH/CH3C(O)OOH | H2O | 1.80332 | 94.3 |
Potentials for 1e− reductions are in V vs SHE. Values for E∘(V vs H2) are in V; −eE∘ is the average free energy for addition. Uncited values of E∘(V vs H2) were calculated from other values in the row using Scheme 2 or eq 18. BDFEs and −ΔG∘/n are in kcal mol−1 and if uncited were calculated from E∘(V vs H2) using eq 18. In many cases the citation associated with a BDFE is for the related BDE, and the tabulated value was calculated using eq 9.
Estimated from electron transfer kinetic data.333
−ΔG∘/n values are average free energies for the overall reaction shown except to form H• [rather than add H2(g)]. See Section 4.