| Abstract
| - Reaction of Me2Si(C5Me4H)Cl with 1 equiv of Li2C2B10H10 in toluene/Et2O gave themonoanionic salt [Me2Si(C5Me4)(C2B10H11)]Li(OEt2)0.5 (1), which could be convenientlyconverted into the dianionic salt [{[(μ-η5):σ-Me2Si(C5Me4)(C2B10H10)]Li(THF)}2Li][Li(THF)4]·THF (2) by treatment with 1 equiv of n-BuLi. 1 reacted with 1 equiv of LnCl3 in THF to give[η5-Me2Si(C5Me4)(C2B10H11)]LnCl3Li(THF)3 (Ln = Nd (3), Sm (4)). 3 could further react with1 equiv of 1 to afford [η5-Me2Si(C5Me4)(C2B10H11)]2Nd(μ-Cl)2Li(OEt2)(THF) (6), which couldalso be prepared from the reaction of NdCl3 with 2 equiv of 1. Partial hydrolysis of 4 resultedin the isolation of the novel cluster [{[η5-Me2Si(C5Me4)(C2B10H11)]Sm}2(μ2-Cl)3(μ3-Cl)4Li(OEt2)2Li(THF)2Sm(μ4-O)]2 (5). Treatment of 1 with 4 equiv of NaNH2 in THF, followed by reactionwith 1 equiv of YbCl3, produced (η5-C5Me4H)2Yb(μ-Cl)2Li(THF)2 (7). An equimolar reactionbetween 2 and NdCl3 yielded the anionic compound [{η5: σ-Me2Si(C5Me4)(C2B10H10)}2Nd][Li(DME)3] (11). Interaction of LnCl3 with 0.5 equiv of 2 resulted in the isolation of thelanthanocene chloride compounds [{η5: σ-Me2Si(C5Me4)(C2B10H10)}LnCl(μ-Cl)]2[Li(S)n]2 (S =THF, n = 4, Ln = Sm (8), Y (9); S = DME, n = 3, Ln = Yb (10)). Reaction of 9 with 2 equivof NaN(SiMe3)2 gave the unsolvated compound [η5: σ-Me2Si(C5Me4)(C2B10H10)]YN(SiMe3)2(12). Treatment of LnI2 with 0.5 equiv of 2 afforded the ionic organolanthanide(II) compounds[{η5: σ-Me2Si(C5Me4)(C2B10H10)}LnI2][Li(DME)3]2 (Ln = Sm (13), Yb (14)). All of these newcompounds were characterized by various spectroscopic data and element analyses. The solid-state structures of compounds 2, 5−7, 10, and 14 were further confirmed by single-crystalX-ray analyses.
- A sterically demanding versatile ligand can prevent the ligand redistribution reactions of lanthanocene chlorides and stabilize the coordinatively unsaturated organolanthanide compounds, leading to a new class of organometallic complexes.
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