Reaction of Me2Si(C5H5)Cl with 1 equiv of Li2C2B10H10 in toluene/ether at 0℃, after hydrolysis, gave Me2Si(C5H5)(C2B10H11) (1) in 79% isolated yield. 1 can be conveniently converted into the monoanion [Me2Si(C5H4)(C2B10H11)]Na (2), the dianion [Me2Si(C5H4)-(C2B10H10)]Li2 (3), and the trianion [Me2Si(C5H4)(C2B10H11)]K3 (4) by treatment with NaH, MeLi, and K metal in THF at room temperature, respectively. 2 reacted with 1 equiv of LnCl3 in THF to give [η5-Me2Si(C5H4)(C2B10H11)]LnCl2(THF)3 (Ln) Nd (5), Sm (6), Er (7), Yb (8)) in good yield. Treatment of LnCl3 with 2 equiv of 2 or reaction of [è5-Me2Si(C5H4)-(C2B10H11)]LnCl2(THF)3 with an equimolar amount of 2 in THF resulted in the isolation of [η5-Me2Si(C5H4)(C2B10H11)]2LnCl(THF)2 (Ln) Nd (9), Sm (10), Y (11), Gd (12), Yb (13)) in good yield. Interaction of 3 with LnCl3 in THF in a molar ratio of 1∶1 or 2∶1 or reaction of [η5-Me2Si(C5H4)(C2B10H11)]2LnCl(THF)2 with 2 equiv of MeLi in THF gave the same compounds [{η5:σ-Me2Si(C5H4)(C2B10H10)}2Ln][Li(THF)4] (Ln) Nd (14), Y (15), Er (16), Yb (17)). Treatment of NdCl3 with an equimolar amount of 4 in THF or reaction of [η5-Me2Si-(C5H4)(C2B10H11)]NdCl2(THF)3 with excess K metal in THF produced [η5:η6-Me2Si(C5H4)-(C2B10H11)]Nd(THF)2 (18). Under similar reaction conditions, however, interaction of LnCl3 (Ln) Sm, Yb) with 4 in THF afforded the organolanthanide(Ⅱ) compounds {[η5:η6-Me2Si-(C5H4)(C2B10H11)]LnII(THF)2}{K(THF)2} (Ln) Sm (20), Yb (21)). The Sm analogue of 18, [η5:η6-Me2Si(C5H4)(C2B10H11)]Sm(THF)2 (19), was prepared from an unprecedented redox reaction of SmI2 with 2 equiv of 2 in THF. Reaction of 19 with excess K metal in THF gave 20. Unlike the SmI2 case, interaction of YbI2 with 2 equiv of 2 in THF gave [η5-Me2Si(C5H4)-(C2B10H11)]2YbII(THF)2 (22). All of these compounds were characterized by various spectroscopic and elemental analyses. The solid-state structures of compounds 5, 8, 9, 10, 14, 15, 16, 17, 19, and 22 were confirmed by single-crystal X-ray analyses. The reaction mechanism of the formation of 19 is also proposed.

Summary: Reaction of Me2Si(C9H7)(C2B10H11) with 4 equiv of NaNH2 in dry THF, followed by treatment with 1 equiv of LnCl3, gave unprecedented tetranuclear clusters of the general formula [{(η5-μ2-C9H6SiMe2NH)-Ln}2(μ3-Cl)(THF)]2(í4-NH)âTHF (Ln) Gd (1), Er (2)) in moderate yield. Their molecular structures have been confirmed by single-crystal X-ray analyses, which represent the first organometallic clusters containing a central μ4-imido group.

Summary: Treatment of Me2Si(C5H5)Cl with Li2C2B10H10 followed by hydrolysis gave the new versatile ligand Me2-Si(C5H5)(C2B10H11) in 79% isolated yield, which can be converted into the monoanion, dianion, and trianion, respectively. It makes possible the synthesis of a wide range of organometallic complexes.

A new amine-functionalized carboranyl-indenyl hybrid ligand shows unique properties in stabilizing various kinds of lanthanocene chloride complexes via increasing steric effects imposed by the coordination of NMe2 to the central metal ion, leading to the isolation of kinetic products and monomeric neutral species. Treatment of Me2SiCl(C9H6CH2CH2NMe2) with 1 equiv of Li2C2B10H10 afforded the monolithium salt [Me2Si(C9H5CH2CH2NMe2)-(C2B10H11)]Li(OEt2) (2). Interaction of 2 with 1 equiv of n-BuLi produced the dilithium salt [Me2Si(C9H5CH2CH2NMe2)(C2B10H10)]Li2(OEt2)2 (3). Treatment of 3 with 1 equiv of YbCl3 gave [{η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)}YbCl2][Li(THF)4] (4). Upon heating, 4 was converted to [{η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)}Yb(μ-Cl)1.5]2[Li(THF)4] (6) and finally to [{η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)}Yb(í-Cl)]2 (7) via the elimination of LiCl. Treatment of 6 or its Sm analogue 5 with 2 equiv of sodium amide gave [η5:η1:ó-Me2-Si(C9H5CH2CH2NMe2)(C2B10H10)]Yb(NHC6H3-2,6-Pri 2) (9) or [η5:η1:σ-Me2Si(C9H5CH2CH2-NMe2)(C2B10H10)]Sm(μ-NHC6H3-2,6-Pri 2)(μ-Cl)Li(THF) (8). An equimolar reaction of SmI2 with 3 generated, after addition of LiCl, [{η5:η1:η6-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)Sm}2-(μ-Cl)][Li(THF)4] (10). In sharp contrast, a less reactive YbI2 reacted with 3 in THF, producing only the salt metathesis product [η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)]Yb(DME) (11). 11 reacted with 1 equiv of 3 to give the ionic complex {[(μ-η5:η2):η1:σ-Me2Si(C9H5CH2CH2-NMe2)(C2B10H10)]2Yb}{Li(THF)2}2 (12). All complexes were characterized by spectroscopic techniques and elemental analyses. Their structures were all further confirmed by singlecrystal X-ray analyses.

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 Me2SiCl(C9H6CH2CH2OMe) with 1 equiv of Li2C2B10H10 in toluene/Et2O afforded the monolithium salt [Me2Si(C9H5CH2CH2OMe)-(C2B10H11)]Li(OEt2) (2). Interaction of 2 with 1 equiv of n-BuLi in Et2O produced the dilithium salt [Me2Si(C9H5CH2CH2OMe)(C2B10H10)]Li2(OEt2)2 (3). Reaction of 3 with 1 equiv of LnCl3 at room temperature gave the complex salts of general formula [{[è5:ó-Me2Si(C9H5CH2CH2-OMe)(C2B10H10)]Ln(THF)(μ-Cl)3Ln[η5:η1:η-e2Si(C9H5CH2CH2OMe)(C2B10H10)]}2{Li(THF)}]-[Li(THF)4] (Ln) Y (4), Yb (5)). Upon heating, 5 was converted into [η5:η1:η-Me2Si(C9H5-CH2CH2OMe)(C2B10H10)]Yb(THF)(μ-Cl)2Yb[η5:η1:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)] (6) by eliminating LiCl. Treatment of 4 or 5 with 2 equiv of group 1 metal amides gave organorare-earth amide complexes [è5:è1:ó-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]Y(NHC6H3-2,5-tBu2)-(μ-Cl)Li(THF)3 (8) or [η5:η1:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]Yb(NHC6H3-2,6-iPr2)(í-Cl)Li(THF)3 (9). An equimolar reaction of SmI2 with 3 in THF generated, after addition of LiCl, [{[è5:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]2Sm}{Li(THF)}]n (10) and [{η5:η1:η6-Me2-Si(C9H5CH2CH2OMe)(C2B10H10)Sm}2(í-Cl)][Li(THF)4] (11). In sharp contrast, a less reactive YbI2 reacted with 3 in THF, producing only salt metathesis product [η5:η1:η-Me2Si(C9H5-CH2CH2OMe)(C2B10H10)]Yb(DME)(THF) (12). 12 reacted with 1 equiv of 3 to give the ionic complex {[(μ-η5:η2):η1:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]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.