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)Å; Mo‐Mo 2.7723(14))Å; Fe‐Cl 2.223(4)Å).

Keywords:

• cubane clusters
• iron
• chalcogenide clusters
• cucurbituril adduct

The financial support of the Spanish Ministerio de Educacion y Ciencia and the EU FEDER Program (Grant CTQ2005‐09270‐C02‐01 (RL) and CTQ2005‐09270‐C02‐02 (RHM), Fundacio Bancaixa‐UJI (project P1.1B2004‐19) and Generalitat Valenciana (Project ACOMP06/241) is gratefully acknowledged. The work was also supported by Presidential Grant for Young Researchers (MD‐7072.2006.3) to MNS. The authors thank the Servei Central D'Instrumentacio Cientifica (SCIC) of the Universitat Jaume I for the ESI‐MS and X‐Ray facilities. We also thank Drs. C. Vicent and A. Virovets for their kind help.