Homolysis of the Ln-N bond: Synthesis, characterization and catalytic activity of organolanthanide(II) complexes with furfuryl- and tetrahydrofurfuryl-functionalized indenyl ligands

A series of new organolanthanide(II) complexes with furfuryl- and tetrahydrofurfuryl-functionalized indenyl ligands were synthesized via one-electron reductive elimination reaction. Treatments of [(Me₃Si)₂N]₃Ln^III(μ-Cl)Li(THF)₃ (Ln = Yb, Eu) with 2 equiv. of C₄H₇OCH₂C₉H₇ (1) or C₄H₃OCH₂C₉H₇ (2), respectively in toluene at moderate high temperatures produced, after workup, the corresponding organolanthanide(II) complexes with formula [η⁵:η¹-(C₄H₇OCH₂C₉H₆)]₂Ln^II (Ln = Yb (5), Ln = Eu (6)) and [η⁵:η¹-(C₄H₃OCH₂C₉H₆)]₂Ln^II (Ln = Yb (7), Ln = Eu (8)) in reasonable to good yields. Treatments of [(Me₃Si)₂N]₃Ln^III(μ-Cl)Li(THF)₃ (Ln = Yb, Eu) with 2 equiv. of C₄H₇OCH₂C₉H₆SiMe₃ (3) or C₄H₃OCH₂C₉H₆SiMe₃ (4), respectively, in toluene at moderate high temperatures afforded, after workup, the corresponding organolanthanide(II) complexes with formula [η⁵:η¹-(C₄H₇OCH₂C₉H₅SiMe₃)]₂Ln^II (Ln = Yb (9), Ln = Eu (10)) and[η⁵:η¹-(C₄H₃OCH₂C₉H₅SiMe₃)]₂Ln^II (Ln = Yb (11), Ln = Eu (12)) in good to high yields. All the compounds were fully characterized by spectroscopic methods and elemental analyses. The structure of complex 9 was additionally determined by single-crystal X-ray analyses. Studies on the catalytic activities of complexes showed that the complexes having silyl group functionalized indenyl ligands have high catalytic activities on ε-caprolactone polymerization. The temperatures, substituted groups on the indenyl ligands of the complexes, and solvents effects on the catalytic activities of the complexes were examined.