Complexes 1-Ln were prepared by the stepwise synthetic route shown in Scheme 1. Analysis of mass balances indicated that all reactions proceed with essentially quantitative conversions, and this was in accord with in situ (5-Ln), and HN(Si i Pr3)2; this product distribution is in accord with deprotonation of a silyl group in situ. The physical separation of these three highly alkane-soluble species proved challenging; as such the mixture was treated with 0.5 eq. of [HNEt3][Al{OC(CF3)3}4] in benzene at 20 °C for 30 min, in order to protonate 5-Ln and generate the target homoleptic Ln(III) bis(amide) complexes 1-Ln. After removal of benzene and NEt3 under vacuum, the oily solid was triturated with n-hexane to give a mixture of 4-Ln, HN(Si i Pr3)2 and solid 1-Ln. Filtration and recrystallization of 4-Ln from hexamethyldisiloxane at -30 °C enabled its separation from HN(Si i Pr3)2.