Molecular CHEVREL-like clusters [(RhPPh3)6(μ3-Se)8] and [Pd6(μ3-Te)8](4-).

[(RhPPh3)6(μ3-Se)8]·0.5en (1; en = ethane-1,2-diamine), obtained by the reaction of [Pb2Se3](2-) anions with [Rh(PPh3)3Cl] in en, represents the first compound comprising a molecular [Rh6] octahedron with all faces capped by Se atoms. Analogous treatment of [Pb2Te3](2-) with [Pd(PPh3)2Cl2] yielded [Li4(en)10][Pd6(μ3-Te)8] (2), the first compound exhibiting a molecular, chalcogen-capped [Pd6] 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.