The synthesis and spectroscopic characterization of the mononuclear uranium complex [((ArO)(3)tacn)U-III(NCCH3)] is reported. The uranium(III) complex reacts with organic azides to yield uranium(IV) azido as well as uranium(V) imido complexes, [((ArO)(3)tacn)U-IV(N-3)] and [((ArO)(3)tacn)U-V(NSi(CH3)(3))]. Single-crystal X-ray diffraction, spectroscopic, and computational studies of this analogous series of uranium tris-aryloxide complexes supported by triazacyclononane are described. The hexadentate, tris-anionic ligand coordinates to the large uranium ion in unprecedented fashion, engendering coordinatively unsaturated and highly reactive uranium centers. The macrocyclic triazacyclononane tris-aryloxide derivative occupies six coordination sites, with the three aryloxide pendant arms forming a trigonal plane at the metal center. DFT quantum mechanic methods were applied to rationalize the reactivity and to elucidate the electronic structure of the newly synthesized compounds. It is shown that the deeply colored uranium(III) and uranium(V) species are stabilized via pi-bonding interaction, involving uranium f-orbitals and the axial acetonitrile and imido ligand, respectively. In contrast, the bonding in the colorless uranium(IV) azido complex is purely ionic in nature. The magnetism of the series of complexes with an [N3O3-N-ax] core structure and oxidation states +III, +IV, and +V is discussed in context of the electronic structures.