[(RhPPh3)(6)(mu(3)-Se)(8)].0.5en (1; en -7 ethane-1,2-diarnine), obtained by the reaction of [Pb2Se3](2-) anions with [Rh(RPh3)(3)Cl] in en, represents the first compound comprising a molecular [Rh-6] octahedron with all faces capped by Se atoms. Analogous treatment of [Pb2Te3](2-) With [Pd(PPh3)(2)Cl-2] yielded [L(i)4(en)(10)][Pd-6(mu(3)-Te)(8)] (2), the first compound exhibiting a molecular, chalcogen-capped [Pd-6] aggregate. Besides syntheses and structures of the title Compounds, we report quantum-chemical calculations to understand the electronic properties of these molecular CHEVREL-like complexes.