Class Ib Ribonucleotide Reductases: Activation of a Peroxido-Mn^IIMn^III to Generate a Reactive Oxo-Mn^IIIMn^IV Oxidant.

ABSTRACT: In the postulated catalytic cycle of class Ib Mn₂ ribonucleotide reductases (RNRs), a Mn^II₂ core is suggested to react with superoxide (O₂^·-) to generate peroxido-Mn^IIMn^III and oxo-Mn^IIIMn^IV entities prior to proton-coupled electron transfer (PCET) oxidation of tyrosine. There is limited experimental support for this mechanism. We demonstrate that [Mn^II₂(BPMP)(OAc)₂](ClO₄) (1, HBPMP = 2,6-bis[(bis(2 pyridylmethyl)amino)methyl]-4-methylphenol) was converted to peroxido-Mn^IIMn^III (2) in the presence of superoxide anion that converted to (μ-O)(μ-OH)Mn^IIIMn^IV (3) via the addition of an H

SUBMITTER: Doyle L 

PROVIDER: S-EPMC10828993 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature