Reaction of the lithium amides [(2-C5H4N)C(CH3){CH2N(Li)SiMe3}(2)](2) (2a) and [(2-C5H4N)C(CH3){CH2N(Li)-SiMe(2)tBu}(2)](2) (2b) with the imidotransition metal complexes [Ti(NtBu)Cl-2(py)(3)], [Ti(N-2,6-C(6)H(3)iPr(2))Cl-2(py)(3)], and [Zr(N-2,6-C(6)H(3)iPr(2))Cl-2(thf)(2)] yielded the five-coordinate imido-titanium and -zirconium complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe2R)(2)}Ti(NR')(py)] (R = Me, R' = tBu: 3a, R = tBu, R' = tBu: 3b, R = Me, R' = 2,6-C(6)H(3)iPr(2): 4a, R = Me, R' = 2,6-C6H3Me2: 4b) and [(kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Zr(N-2,6-C(6)H(3)iPr(2))(py)] (5). The tridentate diamido-pyridine ligand adopts a facial coordination mode in the distorted trigonal bipyramidal complexes with the imido ligand occupying an equatorial position, as was established by X-ray diffraction for 3a and 5. Sublimation of 3a and 4a yielded the pure four-coordinate imidotitanium complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NR')] (R' = tBu: 6, 2,6-C(6)H(3)iPr(2): 7) which were structurally characterized by X-ray crystallography. Reaction of 3a with the Lewis acid B(C6F5)(3) also led to abstraction of the axially bound pyridine ligand and the formation of the adduct [py-B(C6F5)(3)] and 6. Reaction of 6 with thf, PMe3, and pyridine led to the formation of pentacoordinate complexes [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}-Ti(NtBu)(thf)] (8), [{kappa N-3-(2-C5H4N)C(CH3)(CH2NSiMe3)(2)}Ti(NtBu)(PMe3)] (9), and [{kappa N-3-(2-C5H4N)C(CH3)(CH2-NSiMe3)(2)}Ti(NtBu)(py)] (3a) in which the donor ligands occupy axial positions.