A manganese(V)-oxo ??-cation radical complex: Influence of one-electron oxidation on oxygen-atom transfer

KAa Prokop, HMa Neu, SPb De Visser, DPa Goldberg

    Research output: Contribution to journalArticlepeer-review

    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 languageEnglish
    Pages (from-to)15874-15877
    Number of pages4
    JournalJournal of the American Chemical Society
    Volume133
    Issue number40
    Publication statusPublished - 2011

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