Treatment of [Cl3Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(/mu(3)-N)}] With [K(C5Me5)] in toluene gives Clo Meio and the paramagnetic [K(mu-Cl)(3)Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (3) derivative. Crystallization of 3 in pyridine affords the potassium-free [Cl-2(py)(2)Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (4) complex. Whereas the reaction of 3 with 1 equiv of 18-crown-6 leads to the molecular complex [(18-crown-6)K(mu-Cl)(3)Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (5), the analogous treatment of 3 with cryptand-222 affords the ion pair [K(crypt-222)][Cl3Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (6). The X-ray crystal structures of 4, 5, and 6 have been determined. Density functional theory (DFT) calculations have elucidated the electronic structure of these species, which should be regarded as containing trivalent Y bonded to the {(mu(3)-NH)(3)Ti-3(eta(5)-Me-5)(3)(mu(3)-N)) metalloligand radical anion.