Several of alkaline-earth-metal complexes [(eta(2):eta(2):mu(N):mu(N)-Li)(+)](2)-[{eta(2)-Me2Si(DippN)(2)} Mg-2](2-) (4), [(eta)2(N,N)-Me2Si(DippN)(2)Ca center dot 3THF] (5), [eta(2)-(N,N)-Me2Si(DippN)(2)Sr center dot THF] (6), and [eta(2)(NN)-Me2Si(DippN)(2)Ba center dot 4THF] (7) of a bulky bis(amido)silane ligand were readily prepared by the metathesis reaction of alkalimetal bis(amido)silane [Me2Si(DippNLi)(2)] (Dipp = 2,6-i-Pr2C6H3) and alkaline-earthmetal halides MX2 (M = Mg, X = Br; M = Ca, Sr, Ba, X = I). Alternatively, compounds 5-7 were synthesized either by transamination of M[N(SiMe3)(2)](2)center dot 2THF (M = Ca, Sr, Ba) and [Me2Si(DippNH)(2)] or by transmetalation of Sn[N(SiMe3)(2)], [Me2Si(DiPPNH)(2)], and metallic calcium, strontium, and barium in situ. The metathesis reaction of dilithium bis(amido)silane [Me2Si(DippNLi)(2)] and magnesium bromide in the presence of oxygen afforded, however, an unusual lithium oxo polyhedral complex {[(DippN-(Me2Si)(2))(mu-O)(Me2Si)](2)(mu-Br)(2)[(mu(3)-Li) center dot THF](4)(mu(4)-O)(4)(mu(3)-Li)(2)} (8) with a squarebasket-shaped core Li6Br2O4 bearing a bis(aminolato)silane ligand. All complexes were characterized using H-1, C-13, and Li-7 NMR and IR spectroscopy, in addition to X-ray crystallography.