The reactions of Me2Si(C9H6CH2CH2-DG)(2), (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N-(CH2CH2)(2)O (4)) with [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) in toluene afforded a series of racemic divalent,rare-earth metal complexes: {eta(5):eta(1):eta(5):eta(1)-Me2Si(C9H5CH2CH2=DG)(2)}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = yb (11) and Eu (12); DG = N(CH2CH2)(2)O, RE = Yb (13) and Eu (14)). Similarly, the raceinic divalent rare-earth metal complexes {eta(5):eta(1):eta(5):eta(1)-Me2Si(C9H5CH2CH2CH2NMe2)-(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H3CH2CH2PMe)(2)Li-2 with NdCl3 gave a racemic dimenc neodymium chloride {eta(5):eta(1):eta(5)-Me2Si(C9H5CH2CH2OMe)(2)NdCl}(2) (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)(2)Li-2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {eta(5):eta(1):eta(5):eta(1)-Me2Si(C9H5CH2CH2NMe2)(2)SmCl}(2)(mu-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {eta(5):eta(1):eta(5):eta(1):sigma-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond alpha-adjacent to the nitrogen atom. Complexes 19 and {eta(5):eta(1):eta(5):eta(1):sigma-Me2Si(C9H5CH2CH2NMe2)-[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)(2)Li-2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.