Synthese und Charakterisierung donor-funktionalisierter ansa-Metallocene von Yttrium,Neodym, Samarium,Erbium und Lutetium |
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Authors: | Herbert Schumann,Frank Erbstein,Jö rg Demtschuk,Roman Weimann |
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Abstract: | Organometallic Compounds of the Lanthanides. 133 Synthesis and Characterization of donor-functionalised ansa -Metallocenes of Yttrium, Neodymium, Samarium, Erbium, and Lutetium The reaction of Me2SiCl2 with K[C5H4tBu], Li[C5H4SiMe3] or K[C5H3tBuMe-3] followed by treatment with K[C5H4CH2CH2NMe2] yields mixed substituted dicyclopentadienyldimethylsilanes which after double deprotonation with KH afford the dipotassium salts K2[Me2Si(C5H3tBu-3)(C5H3CH2CH2NMe2-3)] ( 1 ), K2[Me2Si · (C5H3SiMe3-3)(C5H3CH2CH2NMe2-3)] ( 2 ), and K2[Me2Si · (C5H2tBu-3-Me-5)(C5H3CH2CH2NMe2-3)] ( 3 ), respectively. The reaction of 1 , 2 , or 3 with LnCl3(THF)x (Ln = Y, La, Nd, Sm, Er, Lu) leads to the complexes [Me2Si(C5H3tBu-3) · (C5H3CH2CH2NMe2-3)]LnCl [Ln = Y ( 4 a ), Sm ( 4 c ), Lu ( 4 e )], [Me2Si(C5H3SiMe3-3)(C5H3CH2CH2NMe2-3)]LnCl [Ln = Y ( 5 a ), Sm ( 5 c ), Lu ( 5 e )], and [Me2Si(C5H2tBu-3-Me-5)(C5H3CH2CH2NMe2-3)]LnCl [Ln = Y ( 6 a ), Nd ( 6 b ), Sm ( 6 c ), Er ( 6 d ), Lu ( 6 e )], respectively. Alkylation of 4 a , 4 c , 5 a , and 6 b , 6 e with LiCH3, LiCH2SiMe3, and LiCH(SiMe3)2 produces the alkylmetallocenes [Me2Si(C5H3tBu-3) · (C5H3CH2CH2NMe2-3)]LnR [R = CH3, Ln = Y ( 7 a ), Sm ( 7 c ); R = CH2SiMe3, Ln = Y ( 8 a )], [Me2Si(C5H3SiMe3-3) · (C5H3CH2CH2NMe2-3)]YCH3 ( 9 a ), and [Me2Si(C5H2tBu3-Me-5)(C5H3CH2CH2NMe2-3)]LnR (R = CH3, Ln = Lu ( 10 e ); R = CH2SiMe3, Ln = Lu ( 11 e ); R = CH(SiMe3)2, Ln = Nd ( 12 b ), Lu ( 12 e )], respectively. All new compounds were characterized by elemental analyses, NMR spectroscopy and mass spectrometry. The molecular structure of 6 c and 6 e was determined by single crystal X-ray structure analysis. |
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Keywords: | ansa-Lanthanidocenes Chiral metallocene complexes Lanthanide alkyl compounds Yttrium Neodymium Samarium Erbium Lutetium |
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