Treatment of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] with alkali-metal bis(trimethylsilyl)amido derivatives [M{N(SiMe3)(2)}] in toluene affords edge-linked double-cube nitrido complexes [M(mu(4)-N)(mu(3)-NH)(2){Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}](2) (M = Li, Na, K, Rb, Cs) or corner-shared double-cube nitrido complexes [M(mu(3)-N)(mu(3)-NH)(5){Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = Na, K, Rb, Cs). Analogous reactions with 1/2 equiv of alkaline-earth bis(trimethylsilyl)amido derivatives [M{N(SiMe3)(2)}(2)-(thf)(2)] give corner-shared double-cube nitrido complexes [M{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = Mg, Ca, Sr, Ba). If 1 equiv of the group 2 amido reagent is employed, single-cube-type derivatives [(thf)(x){(Me3Si)(2)N}M- {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Mg, x = 0; M = Ca, Sr, Ba, x = 1) can be isolated or identified. The tetrahydrofuran molecules are easily displaced with 4-tert-butylpyridine in toluene, affording the analogous complexes [(tBupy){(Me3Si)(2)N}M{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Ca, Sr). The X-ray crystal structures of [M(mu(3)-N)(mu(3)-NH)(5){Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = K, Rb, Cs) and [M{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = Ca, Sr) have been determined. The properties and solid-state structures of the azaheterometallocubane complexes bearing alkali and alkaline-earth metals are discussed.