The effect of the catalyst structure on the stereoselectivity of CO/vinyl arene copolymerization has been studied with the aim of developing catalytic systems able to improve the yields while maintaining the high degree of copolymer isotacticity previously obtained using achiral nitrogen ligands. Aryl α-diimine ligands having extended aromatic rings (Ar)2DABMe2, with Ar = 1-C10H7 (e), 1-C14H9 (f), 9-C14H9 (g), have been synthesized, and α-diimine coordination to cationic methylpalladium complexes has been investigated in solution, by means of NMR spectroscopy, and in the solid state for [Pd(Me)(NCMe)((9-C14H9) 2DABMe2)][PF6] (2g). The performance of these catalysts in CO/vinyl arene copolymerization, under mild conditions, was analyzed in terms of productivity and degree of stereoregularity of the resulting polyketones. In comparison with previous results, a remarkable enhancement in the yield of isotactic copolymer was observed using the new achiral 9-anthryl α-diimine ligand g, confirming that the ortho disubstitution and the extended aromatic rings play key roles in obtaining good stereoselectivity and good productivity. To perform a structural analysis of the first steps of the CO/p-methylstyrene copolymerization, complex [Pd(Me)(CO)((9-C14H9)2DABMe2)] [BAr′4] (3g) was used as a starting point: NMR investigation reveals the stereoselective formation of the olefin/CO/olefin insertion product (6g), which prevalently exists in solution in only one diastereoisomeric form, thus justifying the observed high polymer isotacticity.
File in questo prodotto:
Non ci sono file associati a questo prodotto.