Previously unanticipated dinitrogen activation is exhibited by the well-known uranium tris(aryloxide) U(ODtbp)(3), U(OC(6)H(3)-Bu(t)(2)-2,6)(3), and the tri-tert-butyl analogue U(OTtbp)(3), U(OC(6)H(2)-Bu(t)(3)-2,4,6)(3), in the form of bridging, side-on dinitrogen complexes U(OAr)(3)(μ-η(2):η(2)-N(2)), for which the tri-tert-butyl N(2) complex is the most robust U(2)(N(2)) complex isolated to date. Attempted reduction of the tris(aryloxide) complex under N(2) gave only the potassium salt of the uranium(III) tetra(aryloxide) anion, K[U(OAr)(4)], as a result of ligand redistribution. The solid-state structure is a polymeric chain formed by each potassium cation bridging two arenes of adjacent anions in an η(6) fashion. The same uranium tris(aryloxides) were also found to couple carbon monoxide under ambient conditions to give exclusively the ynediolate OCCO dianion in U(OAr)(3)(μ-η(1):η(1)-C(2)O(2)), in direct analogy with the reductive coupling recently shown to afford U{N(SiMe(3))(2)}(3)(μ-η(1):η(1)-C(2)O(2)). The related U(III) complexes U{N(SiPhMe(2))(2)}(3) and U{CH(SiMe(3))(2)}(3) however do not show CO coupling chemistry in our hands. Of the aryloxide complexes, only the U(OC(6)H(2)-Bu(t)(3)-2,4,6)(3) reacts with CO(2) to give an insertion product containing bridging oxo and aryl carbonate moieties, U(2)(OTtbp)(4)(μ-O)(μ-η(1):η(1)-O(2)COC(6)H(2)-Bu(t)(3)-2,4,6)(2), which has been structurally characterized. The presence of coordinated N(2) in U(OTtbp)(3)(N(2)) prevents the occurrence of any reaction with CO(2), underscoring the remarkable stability of the N(2) complex. The di-tert-butyl aryloxide does not insert CO(2), and only U(ODtbp)(4) was isolated. The silylamide also reacts with carbon dioxide to afford U(OSiMe(3))(4) as the only uranium-containing material. GGA and hybrid DFT calculations, in conjunction with topological analysis of the electron density, suggest that the U-N(2) bond is strongly polar, and that the only covalent U→N(2) interaction is π backbonding, leading to a formal (U(IV))(2)(N(2))(2-) description of the electronic structure. The N-N stretching wavenumber is preferred as a metric of N(2) reduction to the N-N bond length, as there is excellent agreement between theory and experiment for the former but poorer agreement for the latter due to X-ray crystallographic underestimation of r(N-N). Possible intermediates on the CO coupling pathway to U(OAr)(3)(μ-C(2)O(2)) are identified, and potential energy surface scans indicate that the ynediolate fragment is more weakly bound than the ancillary ligands, which may have implications in the development of low-temperature and pressure catalytic CO chemistry.