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

Abstract

react with the lithium, sodium, and potassium salts of 1-(but-3-enyl)-2,3,4,5-tetramethylcyclopentadiene, yielding [(CH 2 dCHCH 2 CH 2 C 5 Me 4 ) 2 LnCl] 2 (Ln ) Y (3a), Sm (3b), Lu (3c)) and (CH 2 dCHCH 2 CH 2 C 5 Me 4 ) 2 Yb (6), respectively. The monomeric THF adducts (CH 2 dCHCH 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 CHdCH 2 ] reacts with SmCl 3 , yielding (CH 2 dCHCH 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 CHdCH 2 ] followed by M[C 5 Me 5 ] (M ) Na, K) gives [(CH 2 dCHCH 2 CH 2 C 5 Me 4 )(C 5 - (9c)). The NaCl adduct (CH 2 dCHCH 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 dCHCH 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 dCHCH 2 CH 2 C 5 Me 4 )(C 5 Me 5 )YCH(SiMe 3 ) 2 (12a), as well as (CH 2 dCHCH 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 CdCHCH 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 CHdCMe 2 ] followed by M[C 5 Me 5 ] (M ) Na, K), yielding [(Me 2 CdCHCH 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 CdCHCH 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.

Base-Free Lanthanoidocenes(II) Coordinated by Bulky Pentabenzylcyclopentadienyl Ligands

“…This bond length falls into the range characteristic for Sm III compounds . The shortening of the Sm–C distances in 6 compared to those in the parent 2 indicates the oxidation of the Sm­(II) to Sm­(III) in the course of the reaction.…”

Butenyl‐Substituted Alkaline‐Earth Metallocenes: A First Step towards Olefin Complexes of the Alkaline‐Earth Metals

“…[3][4][5] The formation of vanadium, [6] niobium, [7] and the yttrium complexes investigated by Casey et al [8][9][10] with non-chelating olefins have until now only been detectable by NMR spectroscopy. Both ourselves and Evans et al have been able to show recently that chelating h 5 ,h 2 -cyclopentadienyl ligands such as C 5 Me 4 CH 2 CH 2 CH = CH 2 [11] or C 5 Me 4 SiMe 2 CH 2 CH = CH 2 [12] in the form of their alkali metal salts form metallocenes with the diiodides of Eu, Sm, and Yb in which the terminal olefin groups of the side chains coordinate to the metal center.…”

Synthesis, structure and some reactions of (C5Me4hex)2Ru2(CO)4

“…Synthesis of the new ligand 1 is an adaptation of the method used by Schumann et al [5] for a similar pent-4-enyl derivative. Nucleophilic attack of hexyllithium on 2,3,4,5-tetramethylcyclopent-2-enone ligand gave the crude compound 1 as a dark yellow oil.…”