The U–O bonds of the uranyl ion [UO22+] are very strong, a situation attributable to involvement of both 6d and 5f orbitals in strong covalent bonding as well as the high oxidation state (+VI) of uranium in this species. Important work in the field has shown that when uranyl undergoes one-electron reduction, the resulting U(V) complexes generally display increased Lewis basicity at the oxo groups and greater reactivity. In this presentation, we will discuss an electrochemical scheme for uranyl activation and oxo-functionalization that relies on heterogeneous electron transfer from electrodes to drive reactivity of uranyl oxo ligands with the moderately Lewis acidic triphenylborane (BPh3). The electro-generation of metastable UV species by one-electron reduction in our selected ligand framework is followed by either mono- or bis-borylation of the uranyl ion, reactivity that has been confirmed by crystallographic studies. Detailed electrochemical, spectrochemical, and spectro-electrochemical experiments have been performed to establish the functionalization sequence involved in accessing these borylated complexes and to compare their redox properties. Our recent work on electrokinetic monitoring of reactivity as well as insights gained from joint computational work will be discussed.

Electrochemical activation of the uranyl ion

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