A series of alkali metal capped cerium(IV) imido complexes, [M(solv)(x)] [Ce = N (3,5-(CF3)(2)C6H3)-(TriNOx)] (M = Li, K, Rb, Cs; solv = TMEDA, THF, Et2O, or DME), was isolated and fully characterized. An X-ray structural investigation of the cerium imido complexes demonstrated the impact of the alkali metal counterions on the geometry of the [Ce=N(3,5-(CF3)(2)C6H3).(TriNOx)](-) moiety. Substantial shortening of the Ce=N bond was observed with increasing size of the alkali metal cation. The first complex featuring an unsupported, terminal multiple bond between a Ce(IV) ion and aligand fragment was also isolated by encapsulation of a Cs+ counterion with 2.2.2-cryptand. This complex shows the shortest recorded Ce=N bond length of 2.077(3) angstrom. Computational investigation of the cerium imido complexes using DFT methods showed a relatively larger contribution of the cerium 5d orbital than the 4f orbital to the Ce=N bonds. The [K(DME)(2)][Ce=N(3,5-(CF3)(2)C6H3)(TriNOx)] complex cleaves the Si-O bond in (Me3Si)(2)O, yielding the [(Me3SiO)Ce-IV(TriNOx)] adduct. The reaction of the rubidium capped imido complex with benzophenone resulted in the formation of a rare Ce(IV) oxo complex, that was stabilized by a supramolecular, tetrameric oligomerization of the Ce=O units with rubidium cations.