YCl 3 , SmCl 3 , and LuCl 3 react with (tetramethylvinylcyclopentadienyl)lithium (1a), yielding (CH 2 dCHC 5 Me 4 ) 2 Ln(µ-Cl) 2 Li(Et 2 O) 2 (Ln ) Y (2a), Sm (2b), Lu (2c)). LuCl 3 and the analogous potassium salt 1b form oligomeric [(CH 2 dCHC 5 Me 4 ) 2 Lu(µ 3 -Cl) 2 K(THF)] n (3). Methylation of the yttrium complex 2a with MeLi gives (CH 2 dCHC 5 Me 4 ) 2 Y(µ-CH 3 ) 2 Li(THF) (4). Hydroboration of the complexes 2a-c with 9-BBN results in the formation of (C 8 H 14 BCH 2 -CH 2 C 5 Me 4 ) 2 Ln(µ-Cl) 2 Li(THF) 2 (Ln ) Y (5a), Sm (5b), Lu (5c)). The reaction of YCl 3 with 2 equiv of K[C 5 H 4 CHdC 6 H 10 ] (6) or K[C 5 H 4 CHdCMe 2 ] (10) affords the dimeric complexes [(C 6 H 10 dCHC 5 H 4 ) 2 Y(µ-Cl)] 2 (7) and [(Me 2 CdCHC 5 H 4 ) 2 Y(µ-Cl)] 2 (11), whereas SmCl 3 reacts with 2 equiv of 6 or 10, yielding the tris(cyclopentadienyl) derivatives (C 6 H 10 dCHC 5 H 4 ) 3 -Sm(THF) ( 9) and (Me 2 CdCHC 5 H 4 ) 3 Sm(THF) (13), respectively. Methylation of 7 with MeLi yields unstable [(C 6 H 10 dCHC 5 H 4 ) 2 Y(µ-CH 3 )] 2 (7a). SmI 2 and 6 react with formation of (C 6 H 10 d CHC 5 H 4 ) 2 Sm(THF) 2 (8). Hydrolysis during crystallization of 11 caused by some water in the solvent leads to decomposition, forming the oxygen-bridged complex [(Me 2 CdCHC 5 H 4 ) 2 Y-(Et 2 O)] 2 (µ-O) (12). The ansa-lanthanidocene chloride [H 2 CdC(CH 2 C 5 H 4 ) 2 ]LuCl(THF) (15) was prepared from LuCl 3 and the new ligand K 2 [H 2 CdC(CH 2 C 5 H 4 ) 2 ] ( 14). The structures of 2a, 3, 5b, 7, and 12 were determined by single-crystal X-ray diffraction.
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