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Characterization of metastable intermediates formed in the reaction between a Mn(II) complex and dioxygen, including a crystallographic structure of a binuclear Mn(III)-peroxo species.


ABSTRACT: Transition-metal peroxos have been implicated as key intermediates in a variety of critical biological processes involving O2. Because of their highly reactive nature, very few metal-peroxos have been characterized. The dioxygen chemistry of manganese remains largely unexplored despite the proposed involvement of a Mn-peroxo, either as a precursor to, or derived from, O2, in both photosynthetic H2O oxidation and DNA biosynthesis. These are arguably two of the most fundamental processes of life. Neither of these biological intermediates has been observed. Herein we describe the dioxygen chemistry of coordinatively unsaturated [Mn(II)(S(Me2)N4(6-Me-DPEN))] (+) (1), and the characterization of intermediates formed en route to a binuclear mono-oxo-bridged Mn(III) product {[Mn(III)(S(Me2)N4(6-M

SUBMITTER: Coggins MK 

PROVIDER: S-EPMC3709604 | biostudies-literature | 2013 Apr

REPOSITORIES: biostudies-literature