Addition of 4 equiv of Li(N=(CBu2)-Bu-t) to VCl3 in THF, followed by addition of 0.5 equiv of 12, generates the homoleptic V(IV) ketimide complex, V(N=(CBu2)-Bu-t)(4) (1), in 42% yield. Similarly, reaction of 4 equiv of Li(N=(CBu2)-Bu-t) with NbCl4(THF)(2) in THF affords the homoleptic Nb(IV) ketimide complex, Nb(N=(CBu2)-Bu-t)(4) (2), in 55% yield. Seeking to extend the series to the tantalum congener, a new Ta(IV) starting material, TaCl4(TMEDA) (3), was prepared via reduction of TaCl5 with Et3SiH, followed by addition of TMEDA. Reaction of 3 with 4 equiv of Li(N=(CBu2)-Bu-t) in THF results in the isolation of a Ta(V) ketimide complex, Ta(Cl)(N=(CBu2)-Bu-t)(4) (5), which can be isolated in 32% yield. Reaction of 5 with Tl(OTf) yields Ta(OTf) (N=(CBu2)-Bu-t)(4) (6) in 44% yield. Subsequent reduction of 6 with Cp*Co-2 in toluene generates the homoleptic Ta(IV) congener Ta(N=(CBu2)-Bu-t)(4) (7), although the yields are poor. All three homoleptic group 5 ketimide complexes exhibit squashed tetrahedral geometries in the solid state, as determined by X-ray crystallography. This geometry leads to a d(x2-y2)(1) (B-2(1) in D-2d) ground state, as supported by DFT calculations. EPR spectroscopic analysis of 1 and 2, performed at X- and Qband frequencies (similar to 9 and 35 GHz, respectively), further supports the B-2(1) ground-state assignment, whereas comparison of 1, 2, and 7 with related group 5 tetra(ary1), tetra(amido), and tetra(alkoxo) complexes shows a higher M-L covalency in the ketimide-metal interaction. In addition, a ligand field analysis of 1 and 2 demonstrates that the ketimide ligand is both a strong a-donor and strong a-acceptor, an unusual combination found in very few organometallic ligands.