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 U^II to U^VI and a very recent example of a U^I 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 ^UE_L(L) that more accurately represent metal-ligand bonding situations than previously existing transition metal derived parameters. Exemplarily, we demonstrate ^UE_L(L) parameters to be useful for the prediction of structure-reactivity correlations in order to activate specific substrate targets.