Organometallic compounds of the lanthanides. 130 - Synthesis and characterization of donor-functionalized ansa-cyclopentadienyl-indenyl and ansa-indenyl-indenyl complexes of yttrium, samarium, thulium, and lutetium

The stepwise reaction of Me2SiCl2 with K[C5H3'BuMe-3] or Li[C9H7] and then with K[C9H6CH2CH2NM2-1] followed by double deprotonation with NaH or LiBu, yields the two dimethylsilicon bridged cyclopentadienyl-indenyl and indenyl -indenyl donor-functionalized ligand systems K-2[(C2H2 'Bu-3-Me -5)SiMe2(1 - C9H5- CH2CH2NMe2-3)] (1), and Li-2[(1-C9H6)SiMe2(1-C9H5CH2CH2NMe2-3)] (2) , respectively. Treatment of 1 with YCl3(THF)(3), SmCl3(THF)(1.77), TmI3(DM E)(3), and LuCl3(THF)(3) gives the mixed ansa-metallocenes [(C5H2 'Bu-3 -Me -5)SiMe2(1- C9H5 CH2CH2NMe2-3)]LnX (X = Cl, Ln = Y (3), Sm (4), Lu (5); X =I, Ln = Tm (6)), re spectively. The reaction of 2 with LuCl3(THF)(3) yield s [(1- C9H6)SiMe2(1-C9H5CH2CH2NMe2-3)]LUCl (7). Compound 4 reacts with LiMe to give the corresponding alkyl derivative [(C5H2 'Bu-3-Me-5)SiMe2(1 -C9H5 CH2CH2NMe2-3)] Sm(CH3) (8). The new complexes were characterized by elemen tal analyses, MS spectrometry, and NMR spectroscopy. The molecular structur es of 5 and 6 were determined by single crystal Xray diffraction.