The selective reduction of molecular oxygen (O2) to hydrogen peroxide (H2O2) or water (H2O) is critical to many biological and energy processes, including respiration and novel fuel cell development. Soluble metallocene-based reductants are frequently employed as outer-sphere electron transfer reagents to study O2 reduction, due to their kinetic stability towards O2 in the absence of catalysts or other mediators. In contrast, there are select examples where ferrocene derivatives will reduce O2 in the presence of strong Bronsted- and main-group Lewis-acids (B, Al) in the absence of additional mediators. Other strong redox-inactive Lewis acids, such as trivalent rare earths, have not displayed this type of reactivity towards O2, although they have been used as stoichiometric additives to dramatically enhance rates of electron transfer in transition-metal mediated chemical O2 reduction reactions. In this poster, we will share our investigations on Lewis-acid/metallocene mediated chemical O2 reduction, and describe the factors which dictate reactivity and product selectivity. Our conclusions are supported through UV-Vis spectrophotometry, kinetics experiments, and theoretical studies.

Investigation of Lewis-acid/metallocene mediated chemical O2 reduction

256th National Meeting (2018)

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