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Synthesis and Structures of the First Cationic Perfluoroaryllanthanoid(n) Complexes

机译:第一种阳离子全氟芳基镧系元素(n)配合物的合成和结构

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摘要

Tetraphenylborate salts of solvated pentafluorophenyllanthanoid(II) cations [Ln(C_6F_5)(thf)_n]~+ (Ln = Eu, n = 6 (1); Ln = Yb, n = 5 (2)) were readily synthesized in high yield by reactions of ytterbium or europium with HgPh(C_6F_5) and Me_3NHBPh_4 in THE The structures of 1-THF and 2 confirmed the existence of well-separated ions and both 1 and 2 show notable thermal stability at room temperature. The cation in 2 was also observed in the remarkable mixed-valent complex [Yb~(II)(C_6F_5)(thf)_5][Yb~(III)(C_6F_5)_2{N-(SiMe_3)_2}_2] (3), fortuitously isolated in low yield from a reaction of ytterbium metal, HgPh(C_6F_5), and HN(SiMe_3)_2 in THF, and which additionally has an unusual bis(pentafluorophenyl)bis{bis(trimethylsilyl)amido)}ytterbate(III) anion. ~(171)Yb-~(19)F coupling has been observed in the low-temperature ~(l71)Yb NMR spectra of 2 and [Yb(C_6F_5)_2(thf)_4].
机译:溶剂化的五氟苯基镧系元素(II)阳离子的四苯基硼酸盐[Ln(C_6F_5)(thf)_n]〜(Ln = Eu,n = 6(1); Ln = Yb,n = 5(2))易于合成通过THE或or与HgPh(C_6F_5)和Me_3NHBPh_4的反应,1-THF和2的结构证实存在分离良好的离子,并且1和2在室温下均显示出显着的热稳定性。在显着的混合价络合物[Yb〜(II)(C_6F_5)(thf)_5] [Yb〜(III)(C_6F_5)_2 {N-(SiMe_3)_2} _2]中也观察到2中的阳离子(3 ),不幸地从from金属,HgPh(C_6F_5)和HN(SiMe_3)_2在THF中的反应中以低收率分离,并且还具有不寻常的双(五氟苯基)双{双(双(三甲基甲硅烷基)酰胺基)} y酸酯(III) )阴离子。在2和[Yb(C_6F_5)_2(thf)_4]的低温〜(171)Yb NMR光谱中观察到〜(171)Yb-〜(19)F偶联。

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