A new series of amidolanthanides have been prepared from the reactions between Ln[N(SiMe3)(2)](3) and the chiral NNO ligands, (S)-2-(pyrrol-2-ylmethyleneamino)-2'-hydroxy-6,6'-dimethyl-1,1'-biphenyl (2H(2)) and (S)-5,5',6,6',7,7',8,8'-octahydro-2-(pyrrol-2-ylmethyleneamino)-2'-hydro xy-1,1'-binaphthyl (3H(2)), which are synthesized from the condensation of pyrrole-2-carboxaldehyde with 1 equiv of (S)-2-amino-2'-hydroxy-6,6'-dimethyl-1,1'-biphenyl or (S)5,5', 6,6', 7,7', 8,8'-octahydro-2-amino-2'-hydroxy-1,1'-binaphthyl, in the presence of molecular sieves at 70 degrees C, respectively. Treatment of 2H(2) with 1 equiv of Ln[N(SiMe3)(2)](3) (Ln = Sm, Yb) in toluene under reflux, followed by recrystallization from a toluene solution, gives the dimeric amido complexes, (2-SmN(SiMe3)(2)}(2)center dot 0.5C(7)H(8) (6 center dot 0.5C(7)H(8)) and (2-YbN(SiMe3)(2)}(2) center dot 1.5C(7)H(8) (8 center dot 1.5C(7)H(8)), in good yields. While under similar reaction conditions, the reaction of 2H(2) with 1 equiv of Y[N(SiMe3)213 leads to the isolation of a mixture of (2-YN(SiMe3)2)2 (7a) and ((2)2Y}Y[N(SiMe3)212 (7b) in 82% total yield; the reaction of 3H(2) with 1 equiv of Ln[N(SiMe3)213 (Ln = Y, Yb) gives the trinuclear complexes, [(3)(2)Ln}(2)LnN(SiMe3)2 center dot 1.5C(7)H(8) (Ln = Y (9 center dot 1.5C(7)H(8)), Yb (10 center dot 11.5C(7)H(8))), in good yields. All compounds have been characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of compounds 2H(2) and 6-10 have been further confirmed by X-ray diffraction analyses. Complexes 6-9 are active catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, affording cyclic amines in good yields with moderate ee values.