Isoselective Polymerization of rac-Lactide by Magnesium Initiators Bearing Achiral Di(2-pyridyl)methyl Substituted...

Reactions of achiral di(2-pyridyl)methyl substituted aminophenols L (2-{N-R³-N-[di(2-pyridyl)methyl]aminomethyl}-4-R¹-6-R²-C₆H₂OH: R¹ = R² = Bu, R³ = Bu (L), R³ = hexyl (L), R³ = cyclohexyl (L); R¹ = R² = cumyl, R³ = Bu (L), R³ = hexyl (L), R³ = cyclohexyl (L)) with {Mg[N(SiMe₃)₂]₂}₂ ([L]:[Mg] = 1:1) afforded a series of magnesium silylamido complexes 1-6. In the solid state, the magnesium center of 3, 4, and 6 is penta-coordinated by the tetradentate aminophenloate ligand and one silylamido ligand to form a seriously distorted square-pyramidal geometry as confirmed by X-ray crystallography diffraction analysis. VT ¹H NMR and ROESY experiments further indicate that these magnesium complexes are also five-coordinated in solutions where the coordination of either of the two pyridyl pendants to the magnesium center is maintained. Complexes 1-6 are highly active toward the ring-opening polymerization of rac-lactide (rac-LA) at r.t. both in toluene and in tetrahydrofuran, capable of polymerizing 500 equiv of monomer to high conversions just within minutes. Among them, complex 3 exhibited the highest iso-stereoselectivity, affording moderately isotactic polylactide in toluene (P_m = 0.75). It is found that the isoselectivities and activities of these magnesium complexes toward the polymerization of rac-LA are closely associated with the substituents at the ortho-position of the phenoxide unit and on the skeleton nitrogen atom of the ligand. On the basis of NMR spectroscopic studies, the formation of isotactic PLAs with dominant stereoblock sequences was witnessed by using these magnesium complexes as initiators, and the inequivalent coordination of two pyridyl pendant arms in these magnesium complexes might be the source of exerting isoselective control.