Synthesis and properties of guanidinate derivatives of rare-earth metals.Molecular structures of the{(Me_3Si)_2NC(NPr~i)_2}_2Y(mu-Cl)_2Li(THF)_2,[{(Me_3Si)_2NC(NPr~i)_2}_2SmCl]_2 and {(Me_3Si)_2NC(NPr~i)_2}Sm(mu~3-BH_4)_2(DME) complexes

摘要

The reaction of anhydrous SmCl_3 with two equivalents of lithium N,N'-diisopropyl-N"-bis(trimethylsilyl)guanidinate in THF afforded the [{(Me_3Si)_2NC(NPr~i)_2}_2SmCl]_2 complex (1) in 82% yield.Analogous reactions with YCl_3 and GdCl_3 produced the ate-complexes {(Me_3Si)_2NC(NPr~i)_2}_2Ln(mu-Cl)_2Li(THF)_2 (Ln = Y (2) and Gd (3)).The structures of complexes 1 and 2 were established by X-ray diffraction.The reaction of complex 1 with NaBH_4 in hexane (20 deg C) followed by treatment with dimethoxyethane yielded the unexpected product,{(Me_3Si)_2NC(NPr~i)_2}Sm(mu~3-BH_4)_2(DME) (5).X-ray diffraction study showed that both boro-hydride ligands in complex 5 are tridentate.