Organometallic compounds of the lanthanides.: 168 -: Lanthanidocene complexes containing sulfur-functionalized cyclopentadienyl ligands

YCl3, SmCl3, and LuCl3 react with 2 equivalents of Na[C5H4CH2CH2SR] (R = Ph (2); Et (3)) yielding (PhSCH2CH2C5H4)(2)LnCl (Ln Y (4a), Sm (4b), Lu (4c)), and (EtSCH2CH2C5H4)(2)LuCl (5), respectively. Methylation of 4a, 4c, and 5 with LiMe produces (PhSCH2CH2C5H4)(2)LnMe (Ln = Y (6a); Lu (6c)) and (EtSCH2CH2C5H4)(2)LuMe (7). YCl3 and LuCl3 react with 1 equivalent of 2 or 3 followed by I equivalent Na[C5Me5] to give (PhSCH2CH2C5H4)(C5Me5)LnCl (Ln = Y (8a); Lu (8c)) and (EtSCH2CH2C5H4)(C5Me5)YCl (9). [(EtSCH2CH2C5H4)(C5Me5)LuCl (10) and 1,10-bipyridine form [(EtSCH2CH2C5H4)(C5Me5)Lu(bipy)](+) [(EtSCH2CH2C5H4)(C5Me5)LuCl2](-) (11). Methylation of 8a, 8c, and 9 with LiMe results in the formation of (PhSCH2CH2C5H4)(C5Me5)LnMe (Ln = Y (12a); Lu (12c)) and (EtSCH2CH2C5H4)(C5Me5)YMe (13). LaCl3 and PrCl3 react with 3 equivalents of 3 affording (EtSCH2CH2C5H4)(3)Ln (Ln = La (14d) and Pr (14e)), while the reaction of YbI2 with 2 equivalents of 3 gives [(EtSCH2CH2C5H4)Yb(SCH2CH2C5H4)](2) (15) along with ethane. The structures of 8c, 11, 14d, and 15 were determined by single-crystal X-ray diffraction.