The activation and two-electron reduction of dioxygen (O2) to peroxide (O22-) is highly desirable for carbon-neutral fuel cell design and energy storage. O2 activation has generally been accomplished via transition-metal catalysis where inner-sphere reduction of O2 occurs at the metal center. More recently, main-group (B, Al) Lewis acids have been used to modulate reduction potentials of bound oxygen species and control electron transfer from soluble metallocene reductants. Rare-earth metal (REM) Lewis acids have also enabled the selective formation of O22-, but only in conjunction with CuII catalysts. We have recently pursued a highly O22--selective oxygen reduction reaction with decamethylferrocene in methanol facilitated by REMs in the absence of a transition metal catalyst. We observe the reaction rates depend on the accessibility of the metal center for O2 binding and not solely the Lewis acidity of the REM triflate. In this talk, we will discuss our recent results focused on the experimental and theoretical mechanistic investigation of this reaction.

Peroxide-selective O2 reduction via metal-coupled electron transfer with rare earth triflates

2019 Fall National Meeting

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