A New Series of Homologous Cluster Complexes [Mo3(M'EPh3)Q4Cl4(H2O)5] (M' = Ni, Pd; E = P, As, Sb; Q = S, Se)

Cluster aqua complexes [Mo3(M'Cl)S4(H2O)9]3+ (M' = Ni, Pd) react with EPh3 (E = P, As, Sb) in HCl/CH3OH to give neutral [Mo3(M'EPh3)S4Cl4(H2O)5] (M' = Pd, E = P (1), E = As (2), E = Sb (3); M' = Ni, E = P (4), E = As (5); E = Sb (6). [Mo3(PdPPh3)Se4Cl4(H2O)5] (7) was also obtained. X‐ray crystal structures were determined for 3, 4 and 5. The role of supramolecular interactions in crystal packing is discussed. ESI‐MS spectra were also studied and were used to follow the coordination of the solvent molecules at Mo sites and to assess relative strength of bonding in the clusters. Thermal properties were studied for 4 and 5. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)