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- Title
A Mn<sup>II</sup>Mn<sup>III</sup>‐Peroxide Complex Capable of Aldehyde Deformylation.
- Authors
Magherusan, Adriana M.; Kal, Subhasree; Nelis, Daniel N.; Doyle, Lorna M.; Farquhar, Erik R.; Que, Lawrence; McDonald, Aidan R.
- Abstract
Ribonucleotide reductases (RNRs) are essential enzymes required for DNA synthesis. In class Ib Mn2 RNRs superoxide (O2.−) was postulated to react with the MnII2 core to yield a MnIIMnIII‐peroxide moiety. The reactivity of complex 1 ([MnII2(O2CCH3)2(BPMP)](ClO4), where HBPMP=2,6‐bis{[(bis(2‐pyridylmethyl)amino]methyl}‐4‐methylphenol) towards O2.− was investigated at −90 °C, generating a metastable species, 2. The electronic absorption spectrum of 2 displayed features (λmax=440, 590 nm) characteristic of a MnIIMnIII‐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 MnIIMnIII‐peroxide complex. Unlike all other previously reported Mn2‐peroxides, which were unreactive, 2 proved to be a capable oxidant in aldehyde deformylation. Our studies provide insight into the mechanism of O2‐activation in Class Ib Mn2 RNRs, and the highly reactive intermediates in their catalytic cycle.
- Subjects
RIBONUCLEOSIDE diphosphate reductase; ALDEHYDES; MANGANESE compounds; ELECTRON paramagnetic resonance spectroscopy; X-ray absorption spectra
- Publication
Angewandte Chemie, 2019, Vol 131, Issue 17, p5774
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201900717