Similarities and Differences in Benzene Reduction with Ca, Sr, Yb and Sm: Strong Evidence for Tetra‐Anionic Benzene

Inverse sandwich complexes of Yb and Sm stabilized by a bulky β‐diketiminate (BDI) ligand have been prepared: (BDI)Ln(η 6 ,η 6 ‐C 6 H 6 )Ln(BDI); Ln=lanthanide. Coordinated benzene ligands can be neutral, di‐anionic or, often controversially discussed, even tetra‐anionic. The formal charge on benzene is correlated to assignment of the metal oxidation state which generally poses a problem. Herein, we take advantage of the structural similarities found when comparing Ca II with Yb II , and Sr II with Sm II complexes. In this work, we found an excellent overlap of the Ca/Yb inverse sandwich structures but a striking difference for the Sr/Sm pair. The much shorter Sm−N and Sm‐C 6 H 6 distances are strong evidence for a Sm III ‐benzene −4 ‐Sm III assignment. This was further supported by NMR spectroscopy, magnetic susceptibility, reactivity and comprehensive computational investigation.