Abstract
One-electron oxidation of Mn V-oxo corrolazine 2 affords 2 +, the first example of a Mn V(O) ??-cation radical porphyrinoid complex, which was characterized by UV-vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2 + allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh 3 and RSR substrates, and 2 + was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2 + and 2 and indicates that the greater electrophilicity of 2 + likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes. ?? 2011 American Chemical Society.
| Original language | English |
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| Pages (from-to) | 15874-15877 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 133 |
| Issue number | 40 |
| Publication status | Published - 2011 |