Reaction of UCl4 with 5 equiv of Li(N=(CBuPh)-Bu-t) generates the homoleptic U(IV) ketimide complex [Li(THF)(2)][U(N=(CBuPh)-Bu-t)(5)] (1) in 71% yield. Similarly, reaction of UCI4 with 5 equiv of Li(N=(CBu2)-Bu-t) affords [Li(THF)][U(N=(CBu2)-Bu-t)(5)] (2) in 67% yield. Oxidation of 2 with 0.5 equiv of I-2 results in the formation of the neutral U(V) complex U(N=(CBu2)-Bu-t)(5) (3). In contrast, oxidation of 1 with 0.5 equiv of I-2, followed by addition of 1 equiv of Li(N=(CBuPh)-Bu-t), generates the octahedral U(V) ketimide complex [Li][U(N=(CBuPh)-Bu-t)(6)] (4) in 68% yield. Complex 4 can be further oxidized to the U(VI) ketimide complex U(N=(CBuPh)-Bu-t)(6) (5). Complexes 1-5 were characterized by X-ray crystallography, while SQUID magnetometry, EPR spectroscopy, and UV-vis-NIR spectroscopy measurements were also preformed on complex 4. Using this data, the crystal field splitting parameters of the f orbitals were determined, allowing us to estimate the amount of f orbital participation in the bonding of 4.