TABLE 5.
Comparison of substrate oxidation rates for FeIII–OH and MnIII–OH complexes
| Complex | Substrate | T (˚C) | k2 | H/D KIE | Ref |
|---|---|---|---|---|---|
| 1-OH | TEMPOH | −40 | 0.33 | 1.4 | a |
| 2-OH | TEMPOH | −40 | 0.32 | 1.7 | a |
| 3-OH | TEMPOH | −40 | 0.37 | 2.7 | a |
| [(TMC-py)Fe(OH)]2+ | TEMPOH | −40 | 7.1 | 6 | 37 |
| (TMP)Fe(OH) | TEMPOH | 25 | 76 | - | 53 |
| [(PyPz)Fe(OH2)(OH)4+ | xanthene | 20 | 2.2 × 103 | 20 | 54 |
| [(Py5)Fe(OH)]2+ | DHA | 25 | 4.3 × 10−4 | 6.3 | 55 |
| [(dpaq)Mn(OH)]+ | TEMPOH | 25 | 0.13 | 1.8 | 56 |
| [(dpaq2Me)Mn(OH)]+ | TEMPOH | −35 | 3.9 | 2.7 | 50 |
| [(dpaq5Cl)Mn(OH)]+ | TEMPOH | −35 | 2.8 | - | 51 |
| [(dpaq5NO2)Mn(OH)]+ | TEMPOH | −35 | 7 | - | 51 |
| [(SMe2N4(tren))-Mn(OH)]+ | TEMPOH | 25 | 2.1 × 103 | 3.1 | 52 |
This work. Abbreviations used: TMC-py = 1-(pyridyl-2′-methyl)-4,8,11-trimethyl-1,4,8,11-tetrazacyclotetradecane, Py5 = (2,6-bis(bis(2-pyridyl)methoxymethane)pyridine, TMP = meso-tetramesitylporphyrinate; PyPz = quaternized tetra-2,3-pyridinoporphyrazine, dpaq = 2-(bis(pyridin-2-ylmethyl)amino)-N-(quinolin-8-yl)acetamidate anion.