Scheme illustrating the synthesis of variously substituted single cubanes [(Tp)MoFe3S4(PEt3)3-n(L/L′)n]0/1- by monosubstitution (2-4, 6-8, 12,13), disubstitution (14-16), and trisubstitution (17) of cluster 1. Monosubstituted clusters are also formed by reductive substrate cleavage (5, 9, 10) with the double cubane [(Tp)2Mo2Fe6S8(PEt3)4]. Also shown is the formation of tricluster 18 from trimethylsilylthiolate cluster 11, which is accessible from 3 by reaction with (Me3Si)2S.