Metallorganische Verbindungen der Lanthanoide. 111. Synthese und Charakterisierung kationischer Metallocen‐Komplexe der Lanthanoide. Röntgenstrukturanalyse von [Cp 2*Yb(THF)2][BPh4]

Kationische Organolanthanoide des Typs [(C5H4R)2Sm(THF)2][BPh4] (R = tBu (1), SiMe3 (2)), [PyrSm(THF)][BPh4] (3) (Pyr* = NC4H2tBu2-2,5), [CpLn-(THF)2[BPh4] (Cp* = C5Me5; Ln = Y (4), Yb (5)) und [(C5Me4Et)2Ln(THF)2][BPh4] (Ln = Y (6), Sm (7)) wurden durch Oxidation der zweiwertigen Metallocene [(C5H4R)2Sm(THF)2] (R = tBu, SiMe3), [PyrSm(THF)], [CpYb(THF)] und [(C5Me4Et)2Sm(THF)] mit Ag[BPh4] und durch Protolyse der Lanthanoidalkomplexe [CpYMe(THF)], [CpYbCH(SiMe3)2] und [(C5Me4Et)2LnCH-(SiMe3)2] (Ln = Y, Sm) mit [NEt3H][BPh4] hergestellt. Die 1H-und 13C-NMR-Spektren der neuen Verbindungen werden diskutiert. 5 kristallisiert in der Raumgruppe P21/c mit a = 10.604(7), b = 21.749(3), c = 19.124(4), A, β = 96.47(4)°, Z = 4 und V = 4383(3) A3 (R = 0.0291 fur 8517 beobachtete Reflexe mit Fo ≥ 4σ (Fo). Organometallic Compounds of the Lanthanoids. 111. Synthesis and Characterization of Cationic Metallocene Complexes of the Lanthanoides. X-Ray Crystal Structure of [CpYb(THF)2][BPh4] Cationic organolanthanoide compounds [(C5H4R)2Sm(THF)2][BPh4] (R = tBu (1), SiMe3 (2)), [PyrSm(THF)][BPh4] (3) (Pyr* = NC4H2tBu2-2,5), [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) A, β = 96.47(4)°, Z = 4 and V = 4383(3) A3 (R = 0.0291 for 8517 observed reflections with Fo ≥ 4σ (Fo).