Stepwise substitution of benzylic CH 2 protons in ortho-metallated N, N- di methyl benzyl amine (dmba) ligands leads to chiral ortho-metallated N, N,α- tri methyl benzyl amine (tmba) and cumyl- N, N- dimethyl amine (cuda) ligands. These larger ligands with less or no acidic protons in benzylic position prove to stabilize some of those homoleptic tris-aryls of the larger (middle) and largest (early) rare-earth metal cations, for which such tris-aryl or tris-dmba complexes could not be synthesized so far. The syntheses, characterization and crystal structures of Li(cuda), (tmba) 2Lu(μ-Cl) 2 ( 1), (tmba) 2Y(μ-Cl) 2 ( 2), Y(tmba) 3 ( 3), Dy(tmba) 3 ( 4), Nd(tmba) 3 ( 5), Sm(tmba) 3 ( 6), and Sm(cuda) 3 ( 7) are reported, trends in complex stability are discussed. Stabilization of homoleptic tris-aryl rare-earth metal complexes (Y, Sm, Dy, Nd, Lu) was achieved when benzylic CH 2 protons in ortho-metallated dimethylbenzylamine (dmba) are substituted by one or two methyl groups (tmba, cuda ligands). Display omitted