Reaction of (DIPP-nacnac)CaN(SiMe3)(2)center dot THF (DIPP-nacnac = CH{(CMe)(2,6-/Pr2C6H3N)}(2)) with NH3 gave the heteroleptic complex (DIPP-nacnac)CaNH2 center dot(NH3)(2) which crystallized as a dimer with bridging NH2- ions. In contrast to other heteroleptic (DIPP-nacnac)calcium amides, (DIPP-nacnac)CaNH2 center dot(NH3)(2) is remarkably stable toward ligand exchange. Reaction of (DIPP-nacnac)CaH-THF with Me3SiCN gave the heteroleptic complex (DIPP-nacnac)CaCN center dot THF that crystallized as a trimer. The CN-ions bridge in a linear fashion between the Ca2+ ions. In a new synthetic route (DIPP-nacnac)CaN(SiMe3)(2)center dot THF reacted with Et3NH+Cl- to give (DIPP-nacnac)CaCl center dot THF, which crystallized as a dimer with bridging Cl- ions. The exceptional stability of these aggregates toward ligand-exchange reactions, which would give insoluble homoleptic Ca(NH2)(2), Ca(CN)(2), or CaCl2, is remarkable and likely due to their multinuclear nature.