Organometallic Compounds of the Lanthanides. 130 [1] Synthesis and Characterization of donor-functionalized ansa-Cyclopentadienyl-Indenyl and ansa-Indenyl-Indenyl Complexes of Yttrium, Samarium, Thulium, and Lutetium

摘要

The stepwise reaction of Me_2SiCl_2 with K[C_5H3 ~tBuMe-3] or Li[C_9H_7] and then with K[C_9H_6CH_2CH_2NMe_2-1)] followed by double deprotonation with NaH or LiBu, yields the two dimethylsilicon bridged cyclopentadienyl-indenyl and indenyl-indenyl donor-functionalized ligand systems K_2[(C_2H_2 ~tBu-3-Me-5)]SiMe_2(1-C_9H-5CH_2CH_2NMe_2-3) (1), and Li_2[(1-C_9H_6)SiME_2(1-C_9H_5CH_2CH_2NMe_2-3)] (2), respectively. Treatment of 1 with YCl_3(THF)_3, SmCl_3(THF)_(1.77), TmI_3(DME)_3, and LuCl_3(THF)_3 gives the mixed ansa-metallocenes [(C_5H_2 ~tBu-3-Me-5)SiME_2(1-C_9H-5CH_2CH_2NMe_2-3)]LnX (X = Cl, Ln = Y (3), Sm (4), Lu(5); X = I, Ln = Tm (6), respectively. The reaction of 2 with LuCl_3(THF)_3 yields [(1-C_9H_6))SiMe_2(1-C_9H-5CH_2CH_2NMe_2-3)]LnCl (7). Compound 4 reacts with LiMe to give the corresponding alkyl derivative [(C_5H_2 ~tBu-3-Me-5)]SiMe_2(1-C_9H-5CH_2CH_2NMe_2-3)]Sm(CH_3) (8). The new complexes were characterized by elemental analyses, MS spectrometry, and NMR spectroscopy. The molecular structures of 5 and 6 were determined by single crystal X-ray diffraction.