| Literature DB >> 21888343 |
Katharine A Prokop1, Heather M Neu, Sam P de Visser, David P Goldberg.
Abstract
One-electron oxidation of Mn(V)-oxo corrolazine 2 affords 2(+), the first example of a Mn(V)(O) π-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.Entities:
Mesh：
Substances：
Year: 2011 PMID： 21888343 DOI： 10.1021/ja2066237
Source DB: PubMed Journal: J Am Chem Soc ISSN： 0002-7863 Impact factor: 15.419