Metallorganische Verbindungen der Lanthanoide. 111. Synthese und Charakterisierung kationischer Metallocen-Komplexe der Lanthanoide. Röntgenstrukturanalyse von [CpYb(THF)2][BPh4]

Organometallic Compounds of the Lanthanoids. 111. Synthesis and Characterization of Cationic Metallocene Complexes of the Lanthanoides. X-Ray Crystal Structure of [Cp Yb(THF)₂][BPh₄] Cationic organolanthanoide compounds [(C₅H₄R)₂Sm(THF)₂][BPh₄] (R = ^tBu ( 1 ), SiMe₃ ( 2 )), [PyrSm(THF)][BPh₄] ( 3 ) (Pyr* = NC₄H₂^tBu₂-2,5), [CpLn(THF)₂][BPh₄] (Cp* = C₅Me₅; Ln = Y ( 4 ), Yb ( 5 )), and [(C₅Me₄Et)₂ Ln(THF)₂][BPh₄] (Ln = Y ( 6 ), Sm ( 7 )) have been synthesized by oxidation of the divalent metallocenes [(C₅H₄R)₂Sm(THF)₂] (R = ^tBu, SiMe₃), [PyrSm(THF)], [CpYb(THF), and [(C₅Me₄Et)₂Sm(THF)] with Ag[BPh₄] and by protolysis of the lanthanoide alkyls [CpYMe(THF)], [CpYbCH(SiMe₃)₂], and [(C₅Me₄Et)₂LnCH(SiMe₃)₂] (Ln = Y, Sm) by [NEt₃H][BPh₄]. The ¹H- and ¹³C-NMR spectra of the new compounds are discussed. 5 crystallizes in the space group P2₁/c with a = 10.604(7), b = 21.749(3), c = 19.124(4) Å, β = 96.47(4)°, Z = 4 and V = 4383(3) ų (R = 0.0291 for 8517 observed reflections with F_o ≥ 4σ (F_o).