The chiral phosphanylamides {N(R-*CHMePh)(PPh2)}(-) and {N(S-*CHMePh)(PPh2)}(-) were introduced into rare earth chemistry. Transmetalation of the enantiomeric pure lithium compounds Li{N(R-*CHMePh)(PPh2)] (1a) and Li N(S-*CHMePh)(PPh2)] (1b) with lanthanide bis(phosphinimino)methanide dichloride [{CH(PPh2NSiMe3)(2)}LnCl(2)](2) in a 2:1 molar ratio in THF afforded the enantiomeric pure complexes [{CH(PPh2NSiMe3)(2)}Ln(Cl){eta(2)-N(R-*CHMePh)-(PPh2)}] (Ln = Er (2a), Yb (3a), Lu (4a)) and [{CH(PPh2NSiMe3)(2)}Ln(Cl){eta(2)-N(S-*CHMePh)(PPh2)}] (Ln = Er (2b), Yb (3b), Lu (4b)). The solid-state structures of 2a and 3a,b were established by single-crystal X-ray diffraction. Attempts to synthesize compounds 3 in a one-pot reaction starting from K{CH(PPh2NSiMe3)(2)}, YbCl3, and 1 resulted in the lithium chloride incorporated complex [{(Me(3)SiNpph(2))(2)CH}Yb(mu-Cl)(2)LiCl(THF)(2)] (5). In an alternative approach to give chiral rare earth compounds in a one-pot reaction la or 1b was reacted with LnCl(3) and K2C8H8 to give the enantiomeric pure cyclooctatetraene compounds [{eta(2)-N(R-*CHMePh)(PPh2)}Ln (eta(8)-C8H8)] (Ln = Y (6a), Er (7a), Yb (8)) and [{eta(2)-N(S-*CHMePh)(PPh2)}Ln(eta(8)-C8H8)] (Ln = Y (6b), Er (7b)). The structures of 6a,b, 7a, and 8 were confirmed by single-crystal X-ray diffraction in the solid state.