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. Author manuscript; available in PMC: 2022 Jun 8.
Published in final edited form as: Chem Rev. 2021 Dec 20;122(1):1–49. doi: 10.1021/acs.chemrev.1c00521

Table 12.

PCET Thermochemistry of Organic Hydroperoxidesa

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
a

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 12H2(g) 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.

b

Estimated from electron transfer kinetic data.333

c

−ΔG/n values are average free energies for the overall reaction shown except to form H [rather than add H2(g)]. See Section 4.