Manganese-dependent enzymes serve diverse biological functions, ranging from the detoxification of reactive oxygen species (manganese superoxide dismutase and catalase), the oxidation of fatty acids (manganese lipoxygenase), to water splitting (the oxygen-evolving complex of photosystem II). In many cases, these enzymatic reactions involve the activation of dioxygen, or one of its reduced derivatives (superoxide or hydrogen peroxide), by an active-site manganese(II) center. While peroxo- and oxo-manganese species are often proposed as intermediates in these processes, the fleeting nature of these species prevents a detailed understanding of geometric and electronic contributions to reactivity. This presentation will describe our on-going efforts to provide insights into these intermediates by examining the spectroscopic properties and reactivity of bio-inspired manganese complexes. A particular focus of the talk will be recent kinetic, spectroscopic, and computational investigations aimed at understanding the properties and reactivity of hydroxo- and peroxo-manganese complexes.

Insights into metalloenzyme function from bio-inspired manganese complexes

253rd National Meeting (2017)

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