Having complex 3 at hand with a reproducible procedure and in decent isolated yield, we investigated its reactivity towards electrophiles. Indeed, the ketenecarboxylate complex 3 presents a polarized lanthanide-carbon bond, which is prone to further functionalization or insertion reactions. It should be noted that, for the two previously reported ketenecarboxylate complexes based on Ln(Cp*)2 (Ln = La, Sm) fragments, no study of their reactivity was described.