Synthesis and Crystal Structure of New Early-Lanthanide Organometallic Clusters

Reaction of Cp*2NdCl·LiCl·2thf (1) with excess catecholborane affords the hexameric cluster (Cp*NdCl2)6(LiCl)3(thf)3 (2) bearing three types of bridging chloride ions. Heating the reaction mixture affords the tetrameric cluster [(Cp*NdCl2)4(μ4‐Cl)]2[LiO2][LiO2*Li2O*O2] (3), which has the first crystal structure with the LiO2+ motif. Reaction of complex 1 or the analogous Sm complex, 4, with pinacolborane affords clusters 5a (Nd) or 5b (Sm), respectively, a second type of hexameric cluster built from two CpNd3Cl5(thf) units bonded by two μ2‐Cl atoms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)