Abstract: | Reactions of dry THF/MeCN solutions of Ca[Re6SCl(Cla)6] with silylated derivatives E(SiMe3)2 (E = PhAs, PSiMe3, HN, O, S) and addition of trialkylphosphine PPr3 afford in high yields and at room temperature either the neutral clusters [Re6SX(PPr3)] ( 1 : X = As, 2 : X = P) or the ionic compounds [Re6SX(PPr3)]2+ · [Re6S6Cl8]2– ( 3 : X = NH, 4 : X = O, 5 : X = S). The compounds 1 – 5 were characterised by X‐ray crystal structure analysis. A di‐substitution reaction occurs on the {Re6SCl}4+ cluster core, where the two inner μ3‐chloro ligands Cli are substituted by X (X = As, P, NH, O, S) and all six terminal chloro ligands Cla are exchanged by terminal PPr3‐ligands. |