A series of cyclooctatetraene bis(phosphinimino)methanide complexes of yttrium and the lanthanides, [{CH(PPh2NSiMe3) 2}Ln(η8-C8H8)] (Ln = Y, Sm, Er, Yb, Lu), were synthesized via three different pathways. The title compounds can be obtained either from [(η-C8H8)-LnI(THF) 3] and K{CH(PPh2NSiMe3)2} or from K2C8H8 and [{CH(PPh2NSiMe 3)2}LnCl2]2. In a third approach the title compounds were synthesized in a one-pot reaction starting from K{CH(PPh2NSiMe3)2}, LnCl3, and K2C8H8. All complexes have been characterized by crystal X-ray diffraction. The solid-state structures of these complexes show that both ligands completely shield the metal center. As a result of the steric crowding, both ligands are slightly asymmetrically attached to the metal. Even though the title compounds are noncharged lanthanide complexes with no obvious leaving group and no coordinated solvent molecules, the compounds were tested as catalysts for the hydroamination/cyclization reaction. A moderate catalytic activity at elevated temperature is observed. © 2005 American Chemical Society.