Addition of 2 equiv of AgOTf to [UO2(Ar(2)nacnac)Cl](2) (Ar(2)nacnac={(2,6-(Pr2C6H3)-C-i)NC(Me)}(2)CH) in the presence of excess pyridine, followed by addition Of Cp2Co, generates the uranyl(V) complex UO2(Ar(2)nacnac)(py)(2) (2), in moderate yield. Complex 2 has proven to be an excellent precursor for the synthesis of other U(V) complexes. Thus, addition of 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), TMEDA, or 1-methylimidazole (Melm) to 2 provides UO2(Ar(2)nacnac)(bipy) (3), UO2(Ar(2)nacnac)(phen) (4), UO2(Ar(2)nacnac)(TMEDA) (5), and UO2(Ar(2)nacnac)(Melm)(2) (6), respectively. Complexes 2-6 have been fully characterized and their structures confirmed by X-ray crystallography. Attempts to form the analogous hexavalent uranyl complexes of bipy, phen, and TMEDA have not been successful. However, reaction Of [UO2(Ar(2)nacnac)Cl](2) with AgOTf and 2 equiv of Melm leads to the isolation of [UO2(Ar(2)nacnac)(Melm)(2)][OTf] (7), which has been fully characterized. Attempts to ligate sulfur donor ligands to either the UO2(Ar(2)nacnac) or the [UO2(Ar(2)nacnac)](+) fragments were unsuccessful.