Redox-active manganese enzymes participate in vital biological processes, including the defense against free radicals, the oxidation of aromatic substrates, and the conversion of nucleotides to deoxynucleotides. In many cases, these enzymatic reactions are initiated through the activation of dioxygen, or one of its reduced derivatives (superoxide or hydrogen peroxide), by an active-site Mn(II) center, forming peroxo-, hydroxo, or oxo-manganese intermediates. In this work, we report our on-going efforts using biomimetic manganese complexes to provide insight into the influences of geometric and electronic structure on the reactivity properties of biomimetic manganese intermediates. In particular, we will discuss recent kinetic, spectroscopic, and computational investigations aimed at understanding the formation and oxidative reactivity of hydroxomanganese(III) and oxomanganese(IV) species. The relevance of these results with respect to bioenergy will be discussed.

Biomimetic inorganic chemistry of manganese: New understanding of intermediates and reactions

248th National Meeting (2014)

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