A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation

Adriana M. Magherusan, Subhasree Kal, Daniel N. Nelis, Lorna M. Doyle, Erik R. Farquhar, Lawrence Que, Aidan R. McDonald

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2 Scopus citations


Ribonucleotide reductases (RNRs) are essential enzymes required for DNA synthesis. In class Ib Mn 2 RNRs superoxide (O 2 .− ) was postulated to react with the Mn II 2 core to yield a Mn II Mn III -peroxide moiety. The reactivity of complex 1 ([Mn II 2 (O 2 CCH 3 ) 2 (BPMP)](ClO 4 ), where HBPMP=2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol) towards O 2 .− was investigated at −90 °C, generating a metastable species, 2. The electronic absorption spectrum of 2 displayed features (λ max =440, 590 nm) characteristic of a Mn II Mn III -peroxide species, representing just the second example of such. Electron paramagnetic resonance and X-ray absorption spectroscopies, and mass spectrometry supported the formulation of 2 as a Mn II Mn III -peroxide complex. Unlike all other previously reported Mn 2 -peroxides, which were unreactive, 2 proved to be a capable oxidant in aldehyde deformylation. Our studies provide insight into the mechanism of O 2 -activation in Class Ib Mn 2 RNRs, and the highly reactive intermediates in their catalytic cycle.

Original languageEnglish (US)
Pages (from-to)5718-5722
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number17
StatePublished - Apr 16 2019


  • Mn Mn -peroxide
  • aldehyde deformylation
  • nucleophilic reactivity
  • ribonucleotide reductases
  • superoxide activation

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

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    Magherusan, A. M., Kal, S., Nelis, D. N., Doyle, L. M., Farquhar, E. R., Que, L., & McDonald, A. R. (2019). A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation Angewandte Chemie - International Edition, 58(17), 5718-5722. https://doi.org/10.1002/anie.201900717