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The dissociation of the anionic guanidinate ligand NC(NMe2)2 promoted by rare-earth metal complexes at room temperature is described. Treatment of CpLnCl2(THF)3 with two equiv. of Li[NC(NMe2)2] in THF at room temperature affords [Cp2Ln(μ-η1:η2-L2)]2 (Ln = Y; L = NC(NMe2)NC(NMe2)2) and CpLn[NC(NMe2)2](μ-η1:η2-L)2LnCp2 (Ln = Dy) in moderated yields, respectively. YCl3 reacts with three equiv. of Li[NC(NMe2)2] under the same conditions to give a trinuclear yttrium guanidinate [(Me2N)2CN]5Y3[μ-NC(NMe2)2]2(μ-η1:η2-L)2 in 63% yield. These reactions show that rare-earth metals can promote a C–N bond cleavage of the guanidine anion [NC(NMe2)2]− at room temperature. All new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were determined through single-crystal X-ray diffraction analysis.
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