Electronic supplementary information
for
Hydrogen atom transfer versus proton coupled electron transfer
mechanism of gallic acid with different peroxy radicals
Dejan Milenković1 · Jelena Đorović1 · Vladimir Petrović2 · Edina Avdović2 · Zoran
Marković1,3*
Fig. S1 SOMOs of the most stable radicals formed from the investigated GA in water
Fig. S2 Optimized structures of transition states for HAT mechanism. The distances between
C=O, O−H and H−O9 bonds are given in pm
Fig. S3 Optimized structures of transition states for PCET mechanism. The distances between
C=O, O−H and H−O9 bonds are given in pm
Fig. S4. Dependence of lnkTST and lnkZCT (M-1 s-1) on reciprocal temperature 1/T (K) in the HAT pathways of GA with peroxy radicals.
Fig. S5. Dependence of lnkTST and lnkZCT (M-1 s-1) on reciprocal temperature 1/T (K) in the PCET pathways of GA with peroxy radicals
Table S1. The imaginary frequencies for the all TSs HAT PCETWater
GA−3O· υi(cm-1)
υi(cm-1)
MP -2597.31 /EP -2603.88 /iPP -3108.10 /tBP -3214.80 /
GA−4O·
MP -2337.03 /EP -2318.43 /iPP -2713.52 /tBP -3256.56 /
GA−3O· Benzene
MP -2215.50 -3052.75EP -2247.66 -3108.38iPP -2483.25 -3166.58tBP -2484.36 -3305.57
GA−4O·
MP -2033.83 -3200.97EP -2111.28 -3216.50iPP -2246.58 -3282.17tBP -2502.26 -3406.97
Table S2. The calculated values of kinetic parameters for the reaction of monoanion of GA (GA−(OO-)−4O·) and free peroxy radicals.
ΔG≠
(kJ/mol)kTST
(M-1 s-1)kZCT
(M-1 s-1) γ
MP 27.9 8.04x107 1.64x109 2.04x101
EP 29.9 3.56x107 1.08x108 1.20x102
iPP 30.3 2.16x106 6.49x108 3.00x102
tBP 39.0 9.00x105 3.67x108 4.02x102