Uranium Tetrakis-Aryloxide Derivatives Supported by Tetraazacyclododecane: Synthesis of Air-Stable, Coordinatively-Unsaturated U(IV) and U(V) Complexes.

We present the synthesis, characterization, and one-electron oxidation of two uranium(IV) complexes, coordinated to the cyclen-anchored tetrakis(aryloxide) ligands tetrakis-hydroxybenzyl-1,4,7,10 tetraazacyclododecane, (R,RArOH)4cyclen; R = tBu, Me. The new uranium(IV) and (V) complexes exhibit an eight-coordinate, tetragonal ligand environment, effecting exceptional stability of the coordinatively unsaturated uranium compounds. Cyclic voltammetry studies reveal redox events ranging from tri- to hexavalent species, covering an electrochemical window of ∼4 V.