702673-57-2Relevant academic research and scientific papers
Sidearm effects. Synthesis, structural characterization, and reactivity of rare earth complexes incorporating a linked carboranyl-indenyl ligand with a tethered oxygen atom
Wang, Shaowu,Li, Hung-Wing,Xie, Zuowei
, p. 2469 - 2478 (2004)
New ether-functionalized carboranyl-indenyl hybrid ligands were prepared. They can prevent lanthanocene chlorides from ligand redistribution reactions and offer samarium(II) complexes unusual reactivities. Treatment of Me 2SiCl(C9H6CH2CH2OMe) with 1 equiv of Li2C2B10H10 in toluene/Et2O afforded the monolithium salt [Me2Si(C 9H5CH2CH2OMe)-(C2B 10H11)]Li(OEt2) (2). Interaction of 2 with 1 equiv of n-BuLi in Et2O produced the dilithium salt [Me 2Si(C9H5CH2CH2OMe)(C 2B10H10)]Li2(OEt2) 2 (3). Reaction of 3 with 1 equiv of LnCl3 at room temperature gave the complex salts of general formula [{[η5: σ-Me2Si(C9H5CH2CH 2-OMe)(C2B10H10)]Ln(THF)(μ-Cl) 3Ln[η5:η1:σ-Me 2Si(C9H5CH2CH2OMe)(C 2B10H10)]}2{Li(THF)}]-[Li(THF)4] (Ln = Y (4), Yb (5)). Upon heating, 5 was converted into [η5: η1:σ-Me2Si(C9H5-CH 2CH2OMe)(C2B10H10)] Yb(THF)(μ-Cl)2Yb[η5:η1:σ- Me2Si(C9H5CH2CH2OMe) (C2B10H10)] (6) by eliminating LiCl. Treatment of 4 or 5 with 2 equiv of group 1 metal amides gave organo-rare-earth amide complexes [η5:η1:σ-Me2Si(C 9H5CH2CH2OMe)(C2B 10H10)]Y(NHC6H3-2,5- tBu2)-(μ-Cl)Li(THF)3 (8) or [η5:η1:σ-Me2Si(C 9H5CH2CH2OMe)(C2B 10H10)]Yb(NHC6H3-2,6- iPr2)(μ-Cl)Li(THF)3 (9). An equimolar reaction of SmI2 with 3 in THF generated, after addition of LiCl, [{[η5:σ-Me2Si(C9H5CH 2CH2OMe)(C2B10H10)] 2Sm}{Li(THF)}]n (10) and [{η5: η1:σ6-Me2-Si(C9H 5CH2CH2OMe)(C2B10H 10)Sm}2(μ-Cl)][Li(THF)4] (11). In sharp contrast, a less reactive YbI2 reacted with 3 in THF, producing only salt metathesis product [η5:η1:σ-Me 2Si(C9H5-CH2CH2OMe(C 2B10H10)]Yb(DME)(THF) (12). 12 reacted with 1 equiv of 3 to give the ionic complex {[(μ-η5: η2):η1:σ-Me2Si(C 9H5CH2CH2OMe)(C2B 10H10)]2Yb}{Li(THF)2}2 (13). All complexes were characterized by various spectroscopic techniques and elemental analyses. The structures of 5, 6, and 8-13 were further confirmed by single-crystal X-ray analyses.
