Disproportionation of H2O2 Mediated by Diiron-Peroxo Complexes as Catalase Mimics
Abstract
:1. Introduction
2. Results and Discussions
2.1. Kinetic Studies on the Formation of Diiron-Peroxo Complexes (5–8)
2.2. Catalase-Like Activity of Peroxo-Diiron Complexes
3. Experimental
3.1. Materials and Methods
3.2. Characterization of Ligands and Their Complexes
3.3. Cyclic Voltammetry
3.4. Generation of Diiron-Peroxo Complexes (5–8)
3.5. Diiron-Peroxo-Mediated Disproportionaton of H2O2
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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Cycles | Yield (5) and (O2)/% | Yield (6)/% | Yield (7)/% | Yield (8)/% |
---|---|---|---|---|
I. | 100 (95) | 100 | 100 | 100 |
II. | 91 (92) | 87 | 48 | 43 |
III. | 73 (78) | 70 | 39 | 20 |
IV. | 61 (64) | 53 | 31 | 13 |
V. | 41 (27) | 36 | 26 | 12 |
Nr. | Complex | T/°C | [1–4]0/mM | [H2O2]0/M | kobs10−2 s−1 | k2/M−1 s−1 |
---|---|---|---|---|---|---|
1 | 1 | 15 | 2 | 0.0243 | 2.12 | 0.87 ± 0.03 |
2 | 1 | 15 | 2 | 0.0367 | 3.15 | 0.86 ± 0.04 |
3 | 1 | 15 | 2 | 0.0489 | 4.07 | 0.83 ± 0.03 |
4 | 1 | 15 | 2 | 0.0734 | 6.76 | 0.92 ± 0.04 |
5 | 1 | 15 | 2 | 0.0979 | 9.04 | 0.92 ± 0.03 |
6 | 2 | 15 | 2 | 0.0243 | 4.45 | 1.83 ± 0.09 |
7 | 2 | 15 | 2 | 0.0367 | 5.83 | 1.58 ± 0.05 |
8 | 2 | 15 | 2 | 0.0489 | 8.44 | 1.72 ± 0.06 |
9 | 2 | 15 | 2 | 0.0734 | 10.5 | 1.43 ± 0.04 |
10 | 2 | 15 | 2 | 0.0979 | 14.45 | 1.48 ± 0.04 |
11 | 3 | 15 | 2 | 0.0243 | 9.22 | 3.79 ± 0.15 |
12 | 3 | 15 | 2 | 0.0367 | 12.64 | 3.44 ± 0.13 |
13 | 3 | 15 | 2 | 0.0489 | 16.95 | 3.46 ± 0.14 |
14 | 3 | 15 | 2 | 0.0734 | 24.61 | 3.35 ± 0.14 |
15 | 3 | 15 | 2 | 0.0979 | 31.07 | 3.17 ± 0.11 |
16 | 4 | 15 | 2 | 0.0243 | 9.25 | 3.81 ± 0.15 |
17 | 4 | 15 | 2 | 0.0367 | 13.17 | 3.59 ± 0.14 |
18 | 4 | 15 | 2 | 0.0489 | 18.48 | 3.78 ± 0.16 |
19 | 4 | 15 | 2 | 0.0734 | 27.07 | 3.69 ± 0.15 |
20 | 4 | 15 | 2 | 0.0979 | 35.83 | 3.66 ± 0.15 |
Nr. | Complex | T/°C | [1–4]0/mM | [H2O2]0/M | kobs/10−3 s−1 | k2/10−2 M−1 s−1 |
---|---|---|---|---|---|---|
1 | 1 | 15 | 0.738 | 0.0243 | 0.358 | 1.47 ± 0.06 |
2 | 1 | 15 | 1.48 | 0.0243 | 0.387 | 1.59 ± 0.07 |
3 | 1 | 15 | 2 | 0.0243 | 0.370 | 1.52 ± 0.06 |
4 | 1 | 5 | 2 | 0.0243 | 0.116 | 0.477 ± 0.02 |
5 | 1 | 10 | 2 | 0.0243 | 0.160 | 0.658 ± 0.03 |
6 | 1 | 20 | 2 | 0.0243 | 0.523 | 2.15 ± 0.11 |
7 | 1 | 25 | 2 | 0.1 | 3.33 | 3.33 ± 0.11 |
8 | 1 | 25 | 2 | 0.2 | 5.57 | 2.79 ± 0.08 |
9 | 1 | 25 | 2 | 0.3 | 10.1 | 3.36 ± 0.09 |
10 | 1 | 25 | 2 | 0.6 | 17.3 | 2.89 ± 0.07 |
11 | 1 | 25 | 2 | 0.9 | 27.1 | 3.01 ± 0.06 |
12 | 1 | 25 | 0.3 | 0.3 | 10.3 | 3.42 ± 0.12 |
13 | 1 | 25 | 0.6 | 0.3 | 10.1 | 3.38 ± 0.11 |
14 | 1 | 25 | 1 | 0.3 | 11.1 | 3.68 ± 0.14 |
15 | 1 | 25 | 1.4 | 0.3 | 9.47 | 3.16 ± 0.13 |
16 | 1 | 10 | 2 | 0.3 | 1.99 | 0.663 ± 0.02 |
17 | 1 | 15 | 2 | 0.3 | 3.63 | 1.21 ± 0.05 |
18 | 1 | 20 | 2 | 0.3 | 6.12 | 2.04 ± 0.08 |
19 | 2 | 15 | 0.738 | 0.0243 | 0.823 | 3.39 ± 0.11 |
20 | 2 | 15 | 1.07 | 0.0243 | 0.692 | 2.85 ± 0.09 |
21 | 2 | 15 | 1.48 | 0.0243 | 0.772 | 3.18 ± 0.10 |
22 | 2 | 15 | 1.77 | 0.0243 | 0.744 | 3.06 ± 0.09 |
23 | 2 | 15 | 2 | 0.0243 | 0.730 | 3.00 ± 0.11 |
24 | 2 | 5 | 2 | 0.0243 | 0.332 | 1.37 ± 0.04 |
25 | 2 | 10 | 2 | 0.0243 | 0.413 | 1.70 ± 0.05 |
26 | 2 | 20 | 2 | 0.0243 | 1.09 | 4.49 ± 0.27 |
27 | 3 | 15 | 0.738 | 0.0243 | 3.92 | 16.1 ± 0.72 |
28 | 3 | 15 | 1.48 | 0.0243 | 4.71 | 19.4 ± 0.62 |
29 | 3 | 15 | 2 | 0.0243 | 4.83 | 19.9 ± 0.68 |
30 | 3 | 5 | 2 | 0.0243 | 2.42 | 9.96 ± 0.35 |
31 | 3 | 10 | 2 | 0.0243 | 3.41 | 14.01 ± 0.63 |
32 | 3 | 20 | 2 | 0.0243 | 8.90 | 36.6 ± 2.01 |
33 | 4 | 15 | 0.738 | 0.0243 | 5.49 | 22.6 ± 0.79 |
34 | 4 | 15 | 1.48 | 0.0243 | 5.44 | 22.4 ± 0.83 |
35 | 4 | 15 | 2 | 0.0243 | 5.75 | 23.8 ± 0.85 |
36 | 4 | 5 | 2 | 0.0243 | 2.89 | 11.9 ± 0.48 |
37 | 4 | 10 | 2 | 0.0243 | 4.20 | 17.3 ± 0.67 |
38 | 4 | 20 | 2 | 0.0243 | 10.2 | 42.01 ± 1.77 |
1 (5) | 2 (6) | 3 (7) | 4 (8) | |
---|---|---|---|---|
Epa(FeII/FeIII)/mV vs. Fc/Fc+ | 655 | 683 | 765 | 783 |
Epc(FeII/FeIII)/(mV vs. Fc/Fc+ | −90 | −223 | −155 | −143 |
ΔE/mV | 745 | 905 | 920 | 925 |
yield/% | 85 | 100 | 92 | 85 |
TON ([S]/[Fe]) | 10.4 | 12.2 | 11.3 | 10.4 |
TOF ([S]/[Fe]/h) | 288 | 418 | 354 | 234 |
k2(cat)/10−2 M−1 s−1 (15 °C) | 1.52 | 3.05 | 19.9 | 23.8 |
EA/kJ mol−1 | 72.3 | 55.9 | 57.5 | 55.5 |
ΔS≠/J mol−1 K−1 | −37.7 | −88.1 | −65.9 | −71.4 |
ΔH≠/kJ mol−1 | 70 | 53.5 | 55 | 53.1 |
ΔG≠/kJ mol−1 | 81 | 78.9 | 74 | 73.7 |
kdecay/10−2s−1 (15 °C) | 0.13 | 0.15 | 1.22 | 1.41 |
kform/M−1 s−1 (15 °C) | 0.93 | 1.43 | 3.16 | 3.66 |
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Lakk-Bogáth, D.; Török, P.; Csendes, F.V.; Keszei, S.; Gantner, B.; Kaizer, J. Disproportionation of H2O2 Mediated by Diiron-Peroxo Complexes as Catalase Mimics. Molecules 2021, 26, 4501. https://doi.org/10.3390/molecules26154501
Lakk-Bogáth D, Török P, Csendes FV, Keszei S, Gantner B, Kaizer J. Disproportionation of H2O2 Mediated by Diiron-Peroxo Complexes as Catalase Mimics. Molecules. 2021; 26(15):4501. https://doi.org/10.3390/molecules26154501
Chicago/Turabian StyleLakk-Bogáth, Dóra, Patrik Török, Flóra Viktória Csendes, Soma Keszei, Beatrix Gantner, and József Kaizer. 2021. "Disproportionation of H2O2 Mediated by Diiron-Peroxo Complexes as Catalase Mimics" Molecules 26, no. 15: 4501. https://doi.org/10.3390/molecules26154501