Rare‐Earth Metal Bis(dimethylsilyl)amide Complexes Supported by Cyclooctatetraenyl Ligands

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Abstract
Monomeric cyclooctatetraenyl rare‐earth metal complexes (COT)LnI(thf)3 were examined by X‐ray structure analysis for Ln = La and Sm being isostructural to the Nd and Ce congeners. Reaction of the lanthanum derivative with excess AlMe3 led to partial thf displacement and dimerization to [(COT)La(μ‐I)(thf)2]2. I–/[N(SiHMe2)2]– salt metathetic ligand exchange involving (COT)LnI(thf)3 (Ln = La, Nd, Sm) and Li[N(SiHMe2)2] did not give putative {(COT)Ln[N(SiHMe2)2](thf)x}. Instead, depending on the metal size, the mixed iodide/amide ate complexes (COT)Ln(μ‐I)2{μ‐N(SiHMe2)2}Ln(COT)][Li(thf)4] (Ln = Nd, Sm) and (COT)La(μ‐I)[μ‐N(SiHMe2)2]2La[μ‐(η2:η8‐COT)]Li(thf)3 were obtained and identified by X‐ray structure analyses. In thf solvent, these heteroleptic complexes undergo ligand redistribution to (COT)Ln[μ‐(η2:η8‐COT)]Li(thf)3, whose solid‐state structures were also analyzed by X‐ray diffraction (Ln = Nd, Sm). Utilization of K[N(SiHMe2)2] afforded alkali‐metal‐free (COT)La[N(SiHMe2)2](thf)2 in good yield, whose monomeric composition was determined by X‐ray structure analysis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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