Several trinuclear titanium complexes bearingamido mu-NHR, imido mu-NR, and nitrido mu(n)-N ligands have been prepared by reaction of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] (1) with 1 equiv of electrophilic reagents ROTf (R = H, Me, SiMe3; OTf = OSO2CF3). Treatment of 1 with triflic acid or methyl triflate in toluene at room temperature affords the precipitation of compounds [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NH2)(OTf)] (2) or [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(mu-NH2)(mu-NMe)(OTf)](3). Complexes 2 and 3 exhibit a fluxional behavior in solution consisting of proton exchange between mu-NH2 and mu-NH groups, assisted by the triflato ligand, as could be inferred from a dynamic NMR spectroscopy study. Monitoring by NMR spectroscopy the reaction course. of 1 with MeOTf allows the characterization of the methylamido intermediate [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NHMe)(OTf)] (4), which readily rearranges to give 3 by a proton migration from the NHMe amido group to the NH imido ligands. The treatment of 1 with 1 equiv of Me3SiOTf produces the stable ionic complex [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NHSiMe3)][OTf] (5) with a disposition of the nitrogen ligands similar to that of 4. Complex 5 reacts with 1 equiv of [K{N(SiMe3)(2)}] at room temperature to give [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-N)(mu-NH)(mu-NHSiMe3)] (6), which at 85 degrees C rearranges to the trimethylsilylimido derivative [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(2)(mu-NHSiMe3)] (7). Treatment of 7 with [K{N(SiMe3)(2)}] affords the potassium derivative [K{(mu(3)-N)(mu(3)-NH)(mu(3)-NiSMe3)Ti-3(eta(C5Me5)-C-5)(3)(mu(3)-N)}] (8), which upon addition of 18-crown-6 leads to the ion pair [K(18-crown-6)] [Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)(mu-NH)(mu-NHSiMe3)] (9). The X-ray crystal structures of 2, 5, 6, and 8 have been determined.