The reactions of 2,6-(R) 2C 6H 3NHSiMe 3 (R = iPr or Et) with excess nBuLi in THF or n-hexane, followed by treatment with LnCl 3, produced different kinds of rare earth metal complexes. Complexes incorporating amido and enolate mixed ligands having the general formula (CH 2 CHO)Ln[2,6-( iPr) 2C 6H 3NSiMe 3] 2(μ-Cl)Li(THF) 3 (Ln = Y( 1), Yb( 2)) were prepared by the reaction of N-trimethylsilyl-2,6-diisopropylaniline 2,6-( iPr) 2C 6H 3NHSiMe 3 with excess nBuLi in THF, followed by treatment with LnCl 3. Complexes with the formula [2,6-(Et) 2C 6H 3NSiMe 3] 2Y(THF)(μ-Cl) 2Li(THF) 2 ( 3) and {[2,6-(Et) 2C 6H 3NSiMe 3] 3YCl}[Li(THF) 4] ( 4) were isolated when 2,6-(Et) 2C 6H 3NHSiMe 3 was treated with nBuLi in n-hexane, followed by treatment with 1/2 or 1/3 equiv. of YCl 3 in THF, respectively. All the structures of the complexes were determined by single-crystal X-ray analyses. Investigation on the reactivity of complexes 1 and 2 towards aromatic aldehydes indicated that the amido ligand of complexes 1 and 2 could selectively react with aromatic aldehydes to afford the disproportionation products of amides and alcohols. The reaction of the lithium amide {[2,6-( iPr) 2C 6H 3](Me 3Si)N}Li with aromatic aldehydes in the presence of a catalytic amount of YCl 3 was also studied.