In the first part of the present thesis, novel heteroatomic Zintl anions and a phenyl-ligated trimetallic cluster anion have been synthesized. In the second part, the reactivity of a known heteroatomic tetrahedral Zintl anion toward transition metal as well as lanthanide metal complexes was investigated, giving rise to a variety of ternary intermetalloid cluster anions. In all of the obtained clusters, the sort of main group element atoms that hold the majority of atoms in the cluster anions seem to determine the geometrical properties. The electronic situations within the cluster anions have been elucidated using quantum chemical investigations. These studies revealed that the cluster anions can be regarded as a Wade-type cluster anion, alloy-like molecular anions with complicated bonding situations or electron precise, fulleranetype Zintl anions. In the latter, magnetic properties are adjustable by the type of incorporated lanthanide ions.