Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion.

Rare-earth metal complexes of the parent benzene tetraanion and neutral inverse-sandwich rare-earth metal arene complexes have remained elusive. Here, we report the first neutral inverse-sandwich rare-earth metal complexes of the parent benzene tetraanion supported by a monoanionic β-diketiminate (BDI) ligand. Reduction of the trivalent rare-earth metal diiodide precursors (BDI)MI ₂ (THF) (BDI = HC(C(Me)N[C ₆ H ₃ -(3-pentyl) ₂ -2,6]) ₂ ; M = Y, 1-Y; M = Sm, 1-Sm) in benzene or para -xylene by potassium graphite yielded the neutral inverse-sandwich rare-earth metal arene complexes [(BDI)M(THF) _n ] ₂ (μ-η ⁶ ,η ⁶ -arene) (M = Y, Sm; arene = benzene, 2-M; arene = para -xylene, 3-M). Single crystal X-ray diffraction, spectroscopic and magnetic characterization studies, together with density functional theory (DFT) calculations confirm that these neutral rare-earth metal arene complexes possess an [M ³⁺ -(arene) ^4- -M ³⁺ ] electronic structure with strong metal-arene δ interactions. The arene exchange reactivity shows that 2-Sm has higher stability than 3-Sm. Furthermore, 2-Sm can behave as a four-electron reductant to reduce unsaturated organic substrates. Particularly, while the reaction of 2-Sm with 1,3,5,7-cyclooctatetraene (COT) yielded (BDI)Sm(η ⁸ -COT) (4-Sm), 2-Sm reacted with 1,4-diphenylbutadiyne to afford (BDI)Sm(η ⁴ -C ₄ Ph ₂ ) (5-Sm), the first rare-earth metallacyclopentatriene complex.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)