Stereoselective polymerization of polar vinyl monomers has been a long-standing challenge because the employed transition-metal catalysts are easily poisoned by polar groups of monomers. In this contribution, a series of β-diketiminato rare-earth metal complexes 1-5 (L1-5 Ln(CH2 SiMe3 )2 (THF)n , Ln=Gd-Lu, Y, and Sc) were successfully synthesized. In combination with AliBu3 and [Ph3 C][B(C6 F5 )4 ], complexes 1 c(Tb)-1 g(Tm) exhibited high activities and excellent isoselectivities for the polymerization of ortho-methoxystyrene (oMOS), in which, the polar methoxy group of oMOS did not poison but activated the polymerization through σ-π chelation to the active species together with the vinyl group. Moreover, the large Gd-attached precursor 1 b showed a higher activity, albeit with a slightly decreased isoselectivity. The small Sc-attached precursor 1 i was completely inert. Meanwhile, the spatial steric arrangement and the coordination mode of the β-diketiminato ligand could clearly affect and even block oMOS polymerization. This work sheds new light on the coordination polymerization of polar monomers.
Keywords: coordination modes; isotacticity; polymerization; rare-earths; self-activation.
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