Organometallic Compounds of the Lanthanides. 183 Lanthanide Benzyl Complexes of the Type [Li(tmeda)2][Ln(CHRSiMe2R′)3Cl] (Ln = Pr, Nd, Sm, Er, Lu; R = Ph, 3,5-Me2C6H3; R′ = Me, tBu, Ph) and [Li(tmeda)]2(μ-Cl)3Ln(CHPhSiMe2tBu)2 (Ln = Er, Lu)

PrCl3, NdCl3, SmCl3, ErCl3, and LuCl3 react with three mole equivalents of [Li(tmeda)][CHPhSiMe3] (1), [Li(tmeda)][CHPhSiMe2tBu] (2), [Li(tmeda)][CHPhSiMe2Ph] (3), and [Li(tmeda)][CH(C6H3Me2‐3,5)SiMe2tBu] (4) forming the ate complexes [Li(tmeda)2][Ln(CHPhSiMe3)3Cl] (Ln = Pr (5a), Nd (6a), Sm (7a)), [Li(tmeda)2][Ln(CHPhSiMe2tBu)3Cl] (Ln = Pr (5b), Nd (6b), Sm (7b)), [Li(tmeda)2][Pr(CHPhSiMe2Ph)3Cl] (5c), and [Li(tmeda)2][Ln(CH(C6H3Me2‐3,5)SiMe2tBu)3Cl] (Ln = Er (8d), Lu (9d)). {[Li(tmeda)]2[Nd(CHPhSiMe3)Cl4]}2 (10) and {[Li(tmeda)][Nd(CHPhSiMe3)Cl3(THF)]}2 (11) crystallize from concentrated ethereal solutions of 6a after addition of pentane. 4 reacts with two equivalents of ErCl3 and LuCl3 yielding [Li(tmeda)]2(μ‐Cl)3Ln(CHPhSiMe2tBu)2 (Ln = Er (12), Lu (13)). Compounds 7a,b, 9d, and 13 have been characterized by 1H and 9d and 13 also by 13C NMR spectroscopy, compounds 6b, 7a, 8d, 9d, 10, 11, 12, and 13 by X‐ray structure analysis.