Reaction of (Ph2N)2Sm(THF)4with Azobenzene: Synthesis, X‐ray Structure and Catalytic Behavior of [(Ph2N)(DME)Sm]2(μ‐η2:η2‐N2Ph2)2

Reaction of divalent (Ph2N)2Sm(THF)4with 1 equiv. of azobenzene in THF and then crystallization of the product in DME‐Et2O mixed solvent produced the complex of [(Ph2N)(DME)Sm]2(μ‐η2:η2‐N2Ph2)2(1) in 65.0% yield. In complex1, azobenzene molecules were reduced to be dianionic Ph2N²⁻₂ ligands, bridging two samarium ions in two η2:η2fashions. One samarium ion was bonded to a DME molecule and a diphenyl amido ligand besides two Ph2N²⁻₂ ligands. The unusual Ln‐η2‐arene close interaction was found for the first time for diphenyl amido lanthanides. Complex1could catalyze the polymerization of methyl methacrylate and acrylonitrile