945487-28-5Relevant academic research and scientific papers
Synthesis and structural characterization of a series of lanthanide(II) amides: Steric effect of amido ligand
Zhou, Liying,Wang, Junfeng,Zhang, Yong,Yao, Yingming,Shen, Qi
, p. 5763 - 5772 (2007)
The synthesis and structures of a series of lanthanide(II) and lanthanide(III) complexes supported by the amido ligand N(SiMe3)Ar were described. Several lanthanide(III) amide chlorides were synthesized by a metathesis reaction of LnCl3 with lithium amide, including {[(C 6H5)(Me3Si)N]2YbCl(THF)} 2·PhCH3 (1), [(C6H3- iPr2-2,6)(SiMe3)N]2YbCl(μ-Cl) Li(THF)3·PhCH3 (4), [(C6H 3-iPr2-2,6)(SiMe3)N]YbCl 2(THF)3 (6), and [(C6H3- iPr2-2,6)(SiMe3)N]2SmCl 3Li2(THF)4 (7). The reduction reaction of 1 with Na-K alloy afforded bisamide ytterbium(II) complex [(C6H 5)(Me3Si)N]2Yb(DME)2 (2). The same reaction for Sm gave an insoluble black powder. An analogous samarium(II) complex [(C6H5)(Me3Si)N]2Sm(DME) 2 (3) was prepared by the metathesis reaction of SmI2 with NaN(C6H5)(SiMe3). The reduction reaction of ytterbium chloride 4 with Na-K alloy afforded monoamide chloride {[(C 6H3-iPr2-2,6)(SiMe 3)N]Yb(μ-Cl)(THF)2}2 (5), which is the first example of ytterbium(II) amide chloride, formed via the cleavage of the Yb-N bond. The same reduction reaction of 7 gave a normal bisamide complex [(C 6H3-iPr2-2,6)(SiMe 3)N]2Sm(THF)2 (8) via Sm-Cl bond cleavage. This is the first example for the steric effect on the outcome of the reduction reaction in lanthanide(II) chemistry. 5 can also be synthesized by the Na/K alloy reduction reaction of 6. All of the complexes were fully characterized including X-ray diffraction for 1-7.
