Organometallic Compounds of the Lanthanides. 156.¹ ω-Alkenyl-Functionalized Cyclopentadienyl Complexes of Yttrium, Samarium, Ytterbium, and Lutetium

Abstract

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 ). 10a, 11a, 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.