Synthesis and X-ray crystal structure of cationic polynuclear hydroxide acetylacetonate lanthanide(III) clusters with homodinuclear or heterodinuclear decacarbonyl hydrides: [HMo2(CO)10]− and [HCrW(CO)10]−

The synthesis and characterization of new polynuclear lanthanide(III) ionic clusters of general formula [Ln 9 (acac) 16 (OH) 10 ] + [Mo 2 (CO) 10 (μ-H)]- (Ln = Sm, Eu, Gd, Dy, Yb) and [Sm 9 (acac) 16 OH) 10 ] + [CrW(CO) 10 (μ-H)] - is reported. The polynuclear complexes, prepared under pure nitrogen atmosphere by interaction of the hydridic metal carbonyls with the β-dichetonate Ln(acac) 3 ·3H 2 O (Ln=Sm, Eu, Gd, Dy, Yb). The new clusters were characterized by elemental analysis, complexometric titration for Ln, atomic absorption for Cr, W and Mo, gas-volumetric analysis for CO, FTIR spectroscopy and single crystal X-ray structure determination of [Sm 9 (acac) 16 (OH) 10 ][Mo 2 (CO) 10 (μ-H)]. The Eu and Yb complexes are isostructural to the Sm one for which, similarly to their homonuclear chromium and tungsten derivative analogues, a square antiprismatic arrangement of eight Sm ions with the ninth at the center of the antiprism has been found.