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Bei der Redaktion eingegangen am 17. Mai 1994. Inhaltsiibersicht. Eine Reihe von Lanthanoid(II1)-amiden zur Bildung der Lanthanoiddiamide [Ln(N(C6HS)(SiMe,)J,(THF),] [Ln = Y (l), La (2), Nd (3), Sm [Li(THF)zgl-Cl)zNd(N(C6H3Mez-2,6)(SiMe,)]z(THF)] (11) und (4), Eu (9, Tb (6), Er (8), Yb (9), Lu (lo)] wurde durch Reak-[ClLn(N(C,H,-iso-Prz-2,6)(SiMe3)]z(THF)] [Ln = Nd (12), Lu tion der entsprechenden Lanthanoidtrichloride, LnC13, mit (13)]. Die neuen Verbindungen wurden durch IH-und "C-LiN(C,H,)(SiMe,) erhalten. Die Umsetzung von NdC13(THF)z NMR-und Massenspektren, die Neodymderivate 3, 11 und 12 und LuCI,(THF), mit den Lithiumsalzen der sterisch anspruchs-durch Rontgenstrukturanalysen charakterisiert. vollen Amide [N(C6H,Rz-2,6)(siMe3)] -(R = Me, iso-Pr) fuhrt Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(II1) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C,H,)(SiMe3)]3(THF)], [L~(THF),(U-C~),N~(N(C,H~M~,-~,~)(S~M~,)]~(THF)], and [C1Nd{N(C,H3-iso-Pr,-2,6)(SiMe3)],(THF)] Abstract. A series of lanthanide(II1) amides [Ln(N(C6HS) .[C1Ln(N(C,H,-iso-Prz-2,6)(SiMe&(THF)] [Ln = Nd (12), Lu (SiMe,)],(THF),] [Ln = Y (l), La (2), Nd (3), Sm (4), Eu (S), (13)], respectively. The IH-and I3C-NMR and mass spectra of Tb (6), Er (8), Yb (9), Lu (lo)] could be prepared by the reaction the new compounds as well as the X-ray crystal structures of the of lanthanide trichlorides, LnCI,, with LiN(C6HS)(SiMe3). neodymium derivatives 3, 11 and 12 are discussed. Treatment of NdC13(THF)z and LuC13(THF), with the lithium salts of the bulky amides [N(C,H3R2-2,6)(SiMe3)]-(R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)zgl-Cl)zNd(N(C6H3Mez-2,6)(SiMe3)Jz(THF)] (11) and nide(II1) complexes; X-ray structures

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Metallorganische Verbindungen der Lanthanoide, 891' 1 Cyclooctatetraenyl-Komplexe der friihen Ubergangsmetalle und Lanthanoide, 6f21 (Cyclooctatetraenyl)[~,~'-bis(trimethylsilyl)benzamidinato]und -[diphenylbis( trimethylsilylimido)phosphinato]-Komplexeder Seltenen Erden; Rontgenstrukturanalyse von (CsHS)Tm[PhC(NSiMe3),](THF), ( CsHs)Lu[4-Me0 C6H4C( NSiMe3),] (THF) und ( C8Hs)Nd[Ph2P(NSiMe3)2 I( THF) Organometallic Compounds of the Lanthanoids. 89111. -Cyclooctatetraenyl Complexes of the Early Transition Metals and Lanthanoids, 6121. -(Cyclooctatetraenyl)[~,~-bis(trimethylsilyl)benzamidinato]-and -[diphenylbis(trimethylsilylimido)phosphinato] Complexes of the Rare Earths: X-Ray Structural Analyses of (C8H,)Tm[PhC(NSiMe3)2](THF), (C8H,)Lu[4-Me0C6H4C(NSiMe&](THF), and (C8H8)Nd[Ph2P(NSiMe3),1(THF) [(C8H8)Ln(p-C1)(THF),], or [(C8H8)Ln(p-03SCF3)(THF)z]2 of [(C,H,)Ln(p-Cl)(THF),], (Ln = Ce, Pr, Nd, Sm) with (Ln = Y, Ce, Pr, Nd, Sm, Tm, Lu) react with Na[4-Li[Ph2P(NSiMe3)2] in THF leads directly to the monomeric RC6H4C(NSiMe3)2] (R = H, OMe, CF3) or Li[PhC(NSiMe3),] compounds (C,H8)Ln[Ph,P(NSiMe3),1(THF) [Ln = Ce (18), Pr to give the monomeric (cyclooctatetraeny1)lanthanide benz-(19), Nd (20), Sm (21)] in good yields. The IH-, I3C-, 31P-and amidinates (CBH8)Ln[4-RC6H4C(NSiMe3),](THF) [R = H, 29Si-NMR and mass spectra of the new compounds as well Ln = Y (l), Ce (4), Pr (6), Nd ( 8 ) , Sm (lO), Tm (12), Lu (15); as the molecular structures of 12, 16, and 20 are discussed. R = OMe, Ln = Y (2), Ce (5), Pr (7), Nd (9), Sm (ll), Tm (13), The Raman spectra of the complexes 1-3, 12, and 14-17 Lu (16); R = CF3, Ln = Y (3), Tm (14), Lu (17)]. The reaction have been studied in detail. Komplexe wie (C8H8)Ce(p-Oz~r)2AlEt2['91, (C8H8)Lu(CH2-SiMe,)(THF),["], (C8H8)Ln(o-C6H4CH2NMe2)(THF) (Ln = Er, Luj[10,201 und (COT)LnI(THF), (Ln = La, Ce, Pr, Nd, Sm; n = 1-3)[11,21]. Die Palette der Cyclooctatetraenyl-(1anthanoid)-Halbsandwich-Komplexe konnte in jungster Zeit durch eine Reihe von Alkoxiden[221, Amiden[23], A l k~l e n [~~] und P y r a~o l y l b o r a t e n [~~~~~] erweitert werden.In einer Reihe fruherer Arbeiten konnten wir zeigen, daI3 sich verschiedene raumerfullende Heteroallyl-Liganden gegenuber den Lanthanoiden wie sterische Cyclopentadienyl-Aquivalente ~e r h a l t e n [~~,~~I .Zu diesen Liganden gehoren die N-silylierten Benzamidinat-Anionen [4-RC6H4C-(NSiMe,),]-(R = H, Me, OMe, CF3, Ph) und das Diimidophosphinat-Anion [Ph2P(NSiMe&-. Da es bereits viele Parallelen zwischen der Lanthanoid-Chemie dieser Ligan-