Assembling Process of Charged Nonanuclear Cationic Lanthanide(III) Clusters Assisted by Dichromium Decacarbonyl Hydride

The reaction of Ln(acac)3·3H2O (Ln = Sm, Eu, Gd, Dy, Yb) with K[Cr2(CO)10(μ-H)] at different molar ratios and solvents leads to the formation of nonanuclear lanthanide hydroxo acetylacetonate complexes of general formula [Ln9(OH)10(acac)16][HCr2(CO)10]. The compounds are isomorphous, and the common cationic cluster core consists of a novel square antiprismatic arrangement of nine Ln atoms connected by μ3, μ4 hydroxo bridges and/or by acetylacetonate ligands as it results from the single-crystal X-ray analysis of the Sm derivative for which the most suitable crystals were obtained.