As the properties of the uranyl cation are strongly dictated by its redox chemistry, strategies to reduce high-valent uranyl(VI) often focus on concurrent functionalization of its very strong and inert U–O bonds. In this talk, we will describe an exploration into the reactivity and cross-reactivity that can occur when formulating oxo-activation strategies with Lewis acids across different solvents and in electrochemically or chemically reducing environments. In acetonitrile, the uranyl(V) monocation [UO<sub>2</sub><sup>+</sup>] can be formed reliably by one-electron reduction. However, treatment of this species with tris(pentafluorophenyl)borane (BCF), an important reagent used with frequent success in the field, leads in our system to disproportionation and unselective reactivity. Conversely, reduction to the U(V) state and reaction with BCF in a non-coordinating solvent, such as dichloromethane, occur with vastly different levels of success depending upon the reduction method (electrochemical vs. chemical) and presence of supporting electrolyte. Our latest results will be discussed, including analysis of products arising from the various reaction conditions studied in this work and insights into these products from joint computational studies.

Reactivity and cross-reactivity in electrochemical activation of the uranyl ion

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