Synthesis and Structural Characterization of Novel Organolanthanide Clusters Containing Amido and Imido Groups

Treatment of Me2Si(C9H7)(C2B10H11) with 4 equiv of NaNH2 in THF, followed by reaction with 1 equiv of LnCl3 at room temperature, afforded [{(η5-μ2-C9H6SiMe2NH)Ln}2(μ3-Cl)(THF)]2(μ4-NH)·nOC4H8 (n = 1, Ln = Gd (Ia), Er (Ib); n = 0, Ln = Dy (Ic)), which represent not only the first examples of organometallic clusters containing a central μ4-imido group but also the first organolanthanide indenyl clusters to be reported. Another type of tetranuclear cluster, [{(η5-C9H6SiMe2)2N}(μ2-NH2)Ln2(THF)2]2(μ3-Cl)2(μ2-Cl)2·THF (Ln = Gd (IIa), Y (IIb)), was obtained if the above reactions were carried out at reflux temperature. This type of cluster can also be prepared by refluxing cluster type I in THF in the presence of NaCl. Treatment of Me2Si(C9H7)(C2B10H11) with 8 equiv of NaNH2 in THF, followed by reaction with 1 equiv of LnCl3 at room temperature, gave the trinuclear clusters [(η5-C9H6SiMe2)2N][μ2,μ2-Me2Si(NH)2](η5-μ2-C9H6SiMe2NH)(μ2-Cl)2Ln3(THF)3 (Ln = Gd (IIIa), Er (IIIb)). These results indicate that NaNH2 serv...