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[(C5H4Bu)-Bu-t], Li[C5H4SiMe3] or K[(C5H3BuM e)-Bu-t-3] followed by treatment with K[C5H4CH2CH2NMe2] yields mixed substi tuted dicyclopentadienyldimethylsilanes which after double deprotonation wi th KH afford the dipotassium salts K-2[Me2Si((C5H3Bu)-Bu-t-3)(C5H3CH2CH2NMe 2-3)] (1), K-2[Me2Si . (C5H3SiMe3-3)(C5H3CH2CH2NMe2-3)] (2), and K-2[Me2Si . ((C5H2Bu)-Bu-t-3-Me-5)(C5H3CH2CH2NMe2-3)] (3), respectively. The reaction of 1, 2, or 3 with LnCl(3)(THF)(x) (Ln = Y, La, Nd, Sm, Er, Lu) leads to t he complexes [Me2Si((C5H3Bu)-Bu-t-3) . (C5H3CH2CH2NMe2-3)]LnCl [Ln = Y (4a) , Sm (4c), Lu (4e)], [Me2Si(C5H3SiMe3-3)(C5H3CH2CH2NMe2-3)]LnCl [Ln = Y (5a ), Sm (5c), Lu (5e)], and [Me2Si((C5H2Bu)-Bu-t-3-Me-5)(C5H3CH2CH2NMe2-3)]Ln Cl [Ln = Y (6a), Nd (6b), Sm (6c), Er (6d), Lu (6e)], respectively. Alkylat ion of 4a, 4c, 5a, and 6b, 6e with LiCH3, LiCH2SiMe3, and LiCH(SiMe3)(2) pr oduces the alkylmetallocenes [Me2Si((C5H3Bu)-Bu-t-3) . (C5H3CH2CH2NMe2-3)]L nR [R = CH3, Ln = Y (7a), Sm (7c); R = CH2SiMe3, Ln = Y (8a)], [Me2Si(C5H3S iMe3-3) . (C5H3CH2CH2NMe2-3)]YCH3 (9a), and [Me2Si((C5H2Bu)-Bu-t-3-Me-5) (C SH3CH2CH2NMe2-3)] LnR (R = CH3, Ln = Lu (10e); R = CH2SiMe3, Ln = Lu (11e); R = CH(SiMe3)(2), Ln = Nd (12b), Lu (12e)], respectively. All new compound s were characterized by elemental analyses, NMR spectroscopy and mass spect rometry. The molecular structure of 6e and 6e was determined by single crys tal X-ray structure analysis.