Abstract A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl- amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me 3 Si) 2 N] 3 Ln (μ-Cl) Li (THF) 3 with 2-(2, 6-Me 2 C 6 H 3 NHCH 2) C 4 H 3 NH (1, 1 equiv) in toluene afforded the ...