Half-sandwich rare-earth metal complexes bearing a C5Me4-C6H4-o-CH2NMe2 ligand: synthesis, characterization and catalytic properties for isoprene, 1-hexene and MMA polymerization

Abstract

A new ortho-dimethylaminomethylphenyl-tetramethylcyclopentadienyl ligand C₅Me₄H-C₆H₄-o-CH₂NMe₂ (HL) and a series of rare-earth metal complexes bearing this ligand were synthesized. Of these complexes, two binuclear alkyl complexes [(C₅Me₄-C₆H₄-o-CH₂N(Me)CH₂-μ)Ln(CH₂SiMe₃)]₂ (Ln = Sc (1a) and Y (1b)) were obtained from the alkane elimination reaction of the free ligand with Ln(CH₂SiMe₃)₃(THF)₂, followed by an intramolecular C–H activation process of a NMe group in the ligand with a CH₂SiMe₃ group, two binuclear dichloro complexes (C₅Me₄-C₆H₄-o-CH₂NMe₂)₂Y₂Cl₄[LiCl(THF)₂] (2a) and [(C₅Me₄-C₆H₄-o-CH₂NMe₂)LuCl(μ-Cl)]₂ (2b) were synthesized by the reaction of anhydrous yttrium or lutetium trichloride with the lithium salt of the ligand LiL, and the binuclear bis(borohydrido) complexes [(C₅Me₄-C₆H₄-o-CH₂NMe₂)Ln(μ-BH₄)BH₄]₂ (Ln = Sm (3a) and Nd (3b)) were synthesized by the reaction of Ln(BH₄)₃(THF)₃ (Ln = Sm and Nd) with the lithium salt of the ligand. The molecular structures of all complexes 1a, 1b, 2a, 2b, 3a and 3b were determined by single-crystal X-ray crystallography. Upon activation with AlR₃/Ph₃CB(C₆F₅)₄, MAO or MMAO, the binuclear alkyl complexes 1a and 1b show good catalytic activity for isoprene cis-1,4 enriched regioselective polymerization and moderate catalytic activity for 1-hexene polymerization. Complexes 3a and 3b were studied as catalysts for methyl methacrylate polymerization reaction under different conditions and were found to show moderate to high catalytic activity.