Metallorganische Verbindungen der Lanthanoide, 89. Cyclooctatetraenyl‐Komplexe der frühen Übergangsmetalle und Lanthanoide, 6. (Cyclooctatetraenyl)[<i>N,N</i>′‐bis(trimethylsilyl)benzamidinato]‐und ‐[diphenylbis(trimethylsilylimido)phosphinato]‐Komplexe der Seltenen Erden; Röntgenstrukturanalyse von (C₈H₈)Tm[PhC(NSiMe₃)₂](THF), (C₈H₈)Lu[4‐MeOC₆H₄C(NSiMe₃)₂](THF) und (C₈H₈)Nd[Ph₂P(NSiMe₃)₂](THF)

Abstract

Organometallic Compounds of the Lanthanoids, 89. – Cyclooctatetraenyl Complexes of the Early Transition Metals and Lanthanoids, 6. – (Cyclooctatetraenyl)[ N,N ′‐bis(trimethylsilyl)benzamidinato]‐ and ‐[diphenylbis(trimethylsilylimido)‐phosphinato] Complexes of the Rare Earths; X‐Ray Structural Analyses of (C 8 H 8 )Tm[PhC(NSiMe 3 ) 2 ](THF), (C 8 H 8 )Lu[4‐MeOC 6 H 4 C(NSiMe 3 ) 2 ](THF), and (C 8 H 8 )Nd[Ph 2 P(NSiMe 3 ) 2 ](THF) [(C 8 H 8 )Ln(μ‐Cl)(THF) 2 ] 2 or [(C 8 H 8 )Ln(μ‐O 3 SCF 3 )(THF) 2 ] 2 (Ln = Y, Ce, Pr, Nd, Sm, Tm, Lu) react with Na[4‐RC 6 H 4 C(NSiMe 3 ) 2 ] (R = H, OMe, CF 3 ) or Li[PhC(NSiMe 3 ) 2 ] to give the monomeric (cyclooctatetraenyl)lanthanide benzamidinates (C 8 H 8 )Ln[4‐RC 6 H 4 C(NSiMe 3 ) 2 ](THF) [R = H, Ln = Y ( 1 ), Ce ( 4 ), Pr ( 6 ), Nd ( 8 ), Sm ( 10 ), Tm ( 12 ), Lu ( 15 ); R = OMe, Ln = Y ( 2 ), Ce ( 5 ), Pr ( 7 ), Nd ( 9 ), Sm ( 11 ), Tm ( 13 ), Lu ( 16 ); R = CF 3 , Ln = Y ( 3 ), Tm ( 14 ), Lu ( 17 )]. The reaction of [(C 8 H 8 )Ln(μ‐Cl)(THF) 2 ] 2 (Ln = Ce, Pr, Nd, Sm) with Li[Ph 2 P(NSiMe 3 ) 2 ] in THF leads directly to the monomeric compounds (C 8 H 8 )Ln[Ph 2 P(NSiMe 3 ) 2 ](THF) [Ln = Ce ( 18 ), Pr ( 19 ), Nd ( 20 ), Sm ( 21 )] in good yields. The 1 H‐, 13 C‐, 31 P‐ and 29 Si‐NMR and mass spectra of the new compounds as well as the molecular structures of 12, 16 , and 20 are discussed. The Raman spectra of the complexes 1–3, 12 , and 14–17 have been studied in detail.