Synthesis, Reactivity, and Structural Characterization of Organolanthanide Compounds Incorporating both Cyclopentadienyl and Carboranyl Groups

Abstract

Reaction of Me2Si(C5H5)Cl with 1 equiv of Li2C2B10H10 in toluene/ether at 0 °C, 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 [η5-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] (...