Neutral tris(trimethylsilylmethyl) complexes [Ln(CH 2SiMe 3) 3(L)] (Ln = Sc ( 1), Lu ( 2)) and cationic bis(trimethylsilylmethyl) complexes [Ln(CH 2SiMe 3) 2(L)(THF)] +[BPh 4] −, (Ln = Sc ( 3), Lu ( 4)) that contain bis(2-methoxyethyl)(trimethylsilyl)amine (L = Me 3SiN(CH 2CH 2OMe) 2) as a neutral, tridentate ligand were synthesized and characterized by NMR spectroscopy. X-ray structural analysis was performed for the scandium complex 1 and exhibited a distorted octahedral coordination geometry with a facially arranged ligand at the neutral scandium center. NMR spectroscopy corroborated the coordination of the tertiary amine function of the ligand to the metal. Complexes 3 and 4 expand the still limited range of cationic rare-earth metal alkyl complexes with known neutral, multidentate ligands.