Organoamido‐ and Aryloxolanthanoids, 15. Organometallic Compounds of the Lanthanoids, 116. Syntheses of Low Coordination Number Divalent Lanthanoid Organoamide Complexes, and the X‐ray Crystal Structures of Bis[(N‐2,6‐diisopropylphenyl)(N‐trimethylsilyl)amido]bi(tetrahydrofuran)samarium(II)and ‐ytterbium(II)

The Mercury(II) amide complex Hg[N(SiMe3)(2,6‐iPr2C6H3)]2 (1) was prepared by reaction of HgBr2 with Li[N(SiMe3) 2,6‐iPr2C6H3)] in diethyl ether solvent. Redox transmetallation reactions of 1 with elemental samarium, europium or ytterbium in THF solvent (THF = tetrahydrofuran), generated the novel divalent complexes Ln[N(SiMe3)(2,6‐iPr2C6H3]2(THF)2 with Ln = Sm (2), Eu (3) and Yb (4). 4 was also synthesized by reaction of elemental ytterbium, HgPh2 and HN(SiMe3)(2,6‐Me3)2]2(THF)2 [Ln = Sm (5), Yb (6)] by reaction of the metals with HgPh2 and HN(SiMe3)2. Thermal desolvation of 4 under high vacuum gave Yb(N)(SiMe3)2,6‐iPr2C6H3)]2 (THF) (7), whereas under identical conditions 6 yielded the solvent‐free complex [Yb[N{SiMe3)2]2]2. (8). The new compounds 1–4 and 7 are hydrocarbon soluble and 171Yb‐NMR spectra were recorded for 4, 6, 7 and 8. X‐ray crystal structure determinations of 2 and 4 revealed four‐coordinate, distorted tetrahedral metal environments augmented by weak Ln…ipso‐C(aryl) interactions.