Anionic [Pd(0)-X]- ate complex were proposed as key intermediates in Pd-catalyzed cross-coupling for decades, but their isolation remained elusive. Herein, a chelating Lewis acidic bis(amidophenolato)silane is introduced as a strong Z-type ligand which enables the characterization of the first anionic [Pd(0)-X]- ate complex. Intriguingly, these compounds and the neutral L-Pd(0) analogs exhibit a square planar coordination that is highly unusual for a d10 metal. Theoretical methods scrutinize …