Nonaqueous Electrochemistry of Uranium Complexes: A Guide to Structure-Reactivity Tuning

Uranium complexes can be stabilized in a wide range of oxidation states, ranging from UII to UVI and a very recent example of a UI complex. This review provides a comprehensive summary of electrochemistry data reported on uranium complexes in nonaqueous electrolyte, to serve as a clear point of reference for newly synthesized compounds, and to evaluate how different ligand environments influence experimentally observed electrochemical redox potentials. Data for over 200 uranium compounds are reported, together with a detailed discussion of trends observed across larger series of complexes in response to ligand field variations. In analogy to the traditional Lever parameter, we utilized the data to derive a new uranium-specific set of ligand field parameters UEL(L) that more accurately represent metal-ligand bonding situations than previously existing transition metal derived parameters. Exemplarily, we demonstrate UEL(L) parameters to be useful for the prediction of structure-reactivity correlations in order to activate specific substrate targets.

Automated summary

This review provides a comprehensive summary of electrochemistry data reported on uranium complexes in nonaqueous electrolyte, serving as a reference for newly synthesized compounds and evaluating the influence of different ligand environments on electrochemical properties. The data for over 200 uranium compounds are reported, along with a discussion on trends observed across complexes in response to ligand field variations. The newly derived uranium-specific ligand field parameters are shown to be useful for predicting structure-reactivity correlations and activating specific substrate targets.