Studies on Iron‐Containing Chalcogenide Clusters with Core M3FeQ4 (M=Mo, W; Q=S, Se)

The reaction between metallic iron and the incomplete cuboidal cluster [Mo3Se4(H2O)9]4+ in 2 M HCl gives the heterobimetallic cuboidal cluster with the new Mo3FeSe4 4+ core (exists in 2 M HCl as [Mo3(FeCl)Se4(H2O)9]3+ (UV/Vis λ (ϵ/M−1 cm−1): 500 sh(1085), 633(1216), 531(738), 880(223)); in 2 M Hpts as [Mo3(FeH2O)Se4(H2O)9]4+ (λ(ϵ/M−1cm−1)): 642(669), 528(1122)). No reaction was observed with [W3Q4(H2O)9]4+ (Q=S, Se). For the sulphur analogue, the structure of the 1∶1 adduct with the cucurbit[6]uril (CuC), {[Mo3(FeCl)S4(H2O)8Cl]pyH⊂CuC[6]}Cl3 · 11.25H2O was determined (Mo‐Fe 2.7067(19)A; Mo‐Mo 2.7723(14))A; Fe‐Cl 2.223(4)A).