Organometallic compounds of the lanthanides. 156.1 ω-Alkenyl-functionalized cyclopentadienyl complexes of yttrium, samarium, ytterbium, and lutetium

YCl 3 , SmCl 3 , LuCl 3 , and YbI 2 react with the lithium, sodium, and potassium salts of 1-(but-3-enyl)-2,3,4,5-tetramethylcyclopentadiene, yielding [(CH 2 =CHCH 2 CH 2 C 5 Me 4 ) 2 LnCl] 2 (Ln = Y (3a), Sm (3b), Lu (3c)) and (CH 2 =CHCH 2 CH 2 C 5 Me 4 ) 2 Yb (6), respectively. The monomeric THF adducts (CH 2 =CHCH 2 CH 2 C 5 Me 4 ) 2 LnCl(THF) (Ln = Y (2a), Sm (2b)) crystallize from hexane. Li[C 5 Me 4 CH 2 CH 2 CH 2 CH=CH 2 ] reacts with SmCl 3 , yielding (CH 2 =CHCH 2 CH 2 CH 2 C 5 -Me 4 ) 2 SmCl(THF) (5b). The reaction of YCl 3 , SmCl 3 , and LuCl 3 with 1 equiv of M[C 5 Me 4 -CH 2 CH 2 CH=CH 2 ] followed by M[C 5 Me 5 ] (M = Na, K) gives [(CH 2 =CHCH 2 CH 2 C 5 Me 4 )(C 5 -Me 5 )LnCl] 2 (Ln = Y (9a), Sm (9b), Lu (9c)). The NaCl adduct (CH 2 =CHCH 2 CH 2 C 5 Me 4 )(C 5 Me 5 )-Y(μ-Cl) 2 Na(Et 2 O) 2 (8a) crystallizes from Et 2 O. The cyclopentadienyllanthanide halides 3a,b and 9b react with LiMe, LiCH(SiMe 3 ) 2 , and LiN(SiMe 3 ) 2 , forming the corresponding unstable alkyl derivatives (CH 2 =CHCH 2 CH 2 C 5 Me 4 ) 2 LnR (Ln = Y, R = Me (10a), CH(SiMe 3 ) 2 (11a); Ln = Sm, R = CH(SiMe 3 ) 2 (11b)), and (CH 2 =CHCH 2 CH 2 C 5 Me 4 )(C 5 Me 5 )YCH(SiMe 3 ) 2 (12a), as well as (CH 2 =CHCH 2 CH 2 C 5 Me 4 ) 2 SmN(SiMe 3 ) 2 (13b). lOa, lla,b, and 12a have been characterized by mass spectrometry, whereas all data of 13b have been obtained. The trichlorides of Y, Sm, and Lu react with 2 equiv of the sodium and potassium salts of 1-(4-methylpent-3-enyl)-2,3,4,5-tetramethylcyclopentadiene, yielding [(Me 2 C=CHCH 2 CH 2 C 5 Me 4 ) 2 -LnCl] 2 (Ln = Y (15a), Sm (15b), Lu (15c)) or with 1 equiv of M[C 5 Me 4 CH 2 CH 2 CH=CMe 2 ] followed by M[C 5 Me 5 ] (M = Na, K), yielding [(Me 2 C=CHCH 2 CH 2 C 5 Me 4 )(C 5 Me 5 )LnCl] 2 (Ln = Y (17a), Sm (17b), Lu (17c)). The monomeric NaCl adduct (Me 2 C=CHCH 2 CH 2 C 5 Me 4 )(C 5 -Me 5 )Lu(μ-Cl) 2 Na(OEt 2 ) 2 (16c) crystallizes from Et 2 O. The structures of 2a,b, 8a, 13b, and 16c were determined by single-crystal X-ray diffraction.