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, Larry Que, Aidan R. McDonald

Research output: Contribution to journalArticle

Abstract

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
Volume58
Issue number17
DOIs
StatePublished - Apr 16 2019

Fingerprint

Peroxides
Aldehydes
Ribonucleotide Reductases
X ray absorption spectroscopy
Oxidants
Superoxides
Mass spectrometry
Paramagnetic resonance
Absorption spectra
DNA
Enzymes
Chemical activation
Oxidoreductases

Keywords

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

PubMed: MeSH publication types

  • Journal Article

Cite this

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

A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation . / Magherusan, Adriana M.; Kal, Subhasree; Nelis, Daniel N.; Doyle, Lorna M.; Farquhar, Erik R.; Que, Larry; McDonald, Aidan R.

In: Angewandte Chemie - International Edition, Vol. 58, No. 17, 16.04.2019, p. 5718-5722.

Research output: Contribution to journalArticle

Magherusan, AM, Kal, S, Nelis, DN, Doyle, LM, Farquhar, ER, Que, L & McDonald, AR 2019, ' A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation ', Angewandte Chemie - International Edition, vol. 58, no. 17, pp. 5718-5722. https://doi.org/10.1002/anie.201900717
Magherusan, Adriana M. ; Kal, Subhasree ; Nelis, Daniel N. ; Doyle, Lorna M. ; Farquhar, Erik R. ; Que, Larry ; McDonald, Aidan R. / A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation In: Angewandte Chemie - International Edition. 2019 ; Vol. 58, No. 17. pp. 5718-5722.
@article{eb9d9b9612e8444f96c5d16cb9355770,
title = "A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation",
abstract = "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.",
keywords = "Mn Mn -peroxide, aldehyde deformylation, nucleophilic reactivity, ribonucleotide reductases, superoxide activation",
author = "Magherusan, {Adriana M.} and Subhasree Kal and Nelis, {Daniel N.} and Doyle, {Lorna M.} and Farquhar, {Erik R.} and Larry Que and McDonald, {Aidan R.}",
year = "2019",
month = "4",
day = "16",
doi = "10.1002/anie.201900717",
language = "English (US)",
volume = "58",
pages = "5718--5722",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "17",

}

TY - JOUR

T1 - A Mn II Mn III -Peroxide Complex Capable of Aldehyde Deformylation

AU - Magherusan, Adriana M.

AU - Kal, Subhasree

AU - Nelis, Daniel N.

AU - Doyle, Lorna M.

AU - Farquhar, Erik R.

AU - Que, Larry

AU - McDonald, Aidan R.

PY - 2019/4/16

Y1 - 2019/4/16

N2 - 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.

AB - 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.

KW - Mn Mn -peroxide

KW - aldehyde deformylation

KW - nucleophilic reactivity

KW - ribonucleotide reductases

KW - superoxide activation

UR - http://www.scopus.com/inward/record.url?scp=85063572902&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85063572902&partnerID=8YFLogxK

U2 - 10.1002/anie.201900717

DO - 10.1002/anie.201900717

M3 - Article

VL - 58

SP - 5718

EP - 5722

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 17

ER -