A series of organometallic pentavalent uranium complexes of the general formula (C5Me5)(2)U(=N-2,6-Pr-i(2)-C6H3)(Y) (Y = monoanionic, non-halide ligand) have been prepared using a variety of routes. Utilizing the direct oxidation of (C5Me5)(2)U(=N-2,6-Pr-i(2)-C6H3)(THF) (2) with the appropriate copper(l) salt yielded the triflate (Y = OTf (OSO2CF3), 11) thiolate (Y = SPh, 12), and acetylide (Y = C CPh, 13) complexes, while a salt metathesis route between the U-V-imido (C5Me5)(2)U(=N-2,6-Pr-i(2)-C6H3)(I) (10) and various alkali salts gave the diphenylamide (Y = NPh2, 14), aryloxide (Y = OPh, 15), alkyl (Y = Me, 16), and aryl (Y = Ph, 17) complexes. Paired with 13, the isolation of 16 and 17 shows that U-V can support the full range of carbon anions (sp, sp(2), and sp(3)), and these are, to the best of our knowledge, the first examples of pentavalent uranium complexes with anionic carbon moieties other than carbocyclic (C5R5, C7H7, C8H8) ligands. Finally, both protonolysis and insertion pathways afforded the U-V-imido ketimide complex (C5Me5)(2)U(=N-2,6-Pr-i(2)-C6H3)(N=CPh2) (18). The complexes have been isolated in good yield and characterized using various combinations of H-1 NMR spectroscopy, elemental analysis, mass spectrometry, single crystal X-ray diffraction, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and magnetic susceptibility measurements, All (C5Me5)(2)U(=N-Ar)(X) (X = F, Cl, Br, I) and (C5Me5)(2)U(=N-Ar)(Y) complexes exhibit U-VI/U-V and U-V/U-IV redox couples by voltammetry. The potential separation between these couples remains essentially constant at similar to 1.50 V, but both processes shift in tandem in potential by similar to 700 mV across the series of X/Y ligands. No significant differences between mu(eff) values or temperature dependencies in the magnetic susceptibility were observed for these complexes regardless of the identity of the ancillary X/Y ligand. However, an excellent linear correlation was observed between the chemical shift values Of C5Me5 ligand protons in the 1H NMR spectra and the oxidation potentials of (C5Me5)(2)U(=N-2,6-Pr-i(2)-C6H3)(X/Y), suggesting that there is a common origin, overall sigma-/pi-donation from the ancillary X/Y ligand to the metal, contributing to both observables. Combined, these data confer the following trend in increasing sigma/pi-donating ability of the X/Y ligand to the U-V metal center: OTf < I < Br < Cl < SPh < C CPh < F < [OPh similar to Me similar to Ph] << NPh2 < N=CPh2. These (C5Me5)(2)U(=N-2,6-Pr-i(2)-C6H3)(X/Y) complexes also show distinct hallmarks of a covalent bonding interaction between the metal and the imide ligand that is modulated to varying degrees by the interaction between the X/Y ancillary ligand and the Uv metal center. These signatures of covalency include stabilization of multile metal oxidations states [U-VI, U-V, and U-IV] and enhanced intensities in the intraconfiguration (f-f) transitions. Of particular note in this regard is the more than 20-fold enhancement in the f-f intensities observed for Y C=CPh and N=CPh2, which is a clear reflection of the covalent metal-ligand bonding interactions sustained by the acetylicle and ketimide ligands in these pentavalent systems.