Stereoselective ROP of rac-Lactide Mediated by Enantiopure NNO-Scorpionate Zinc Initiators
The reaction of the enantiopure NNO-scorpionate ligand (R,R)-bpzmmH with [ZnR2] (R = Me, Et, CH2SiMe3) in a 1:2 molar ratio afforded the dinuclear tris-alkyls [Zn(R)(κ2-NNμ-O)Zn(R)2] (R = Me (1), Et (2), CH2SiMe3 (3)). The reaction of the bimetallic tris-alkyls 1–3 with an aromatic alcohol and thioalcohol yielded the dinuclear zinc complexes containing aryloxide/arylthioxide ligands [(ZnR)2(κN:κN-μ-O)(μ-EAr)] (Ar = 2,6-C6H3Me2; E = O, R = Me (4), Et (5), CH2SiMe3 (6); E = S, R = Me (7), Et (8), CH2SiMe3 (9)) by an alcoholysis or thioalcoholysis reaction. The structures of the different compounds were determined by spectroscopic methods and, in addition, the X-ray crystal structures of 2 and 5 were also unambiguously established. Alkyl- and aryloxide/thioaryloxide-containing enantiopure zinc complexes 3–6 and 9 can act as single-component living initiators for the ring-opening polymerization of lactides, affording materials with low molecular weights under mild conditions in only a few hours. Interestingly, microstructural analysis of poly(rac-lactide) by 1H NMR spectroscopy revealed that the most sterically hindered initiator, [(ZnCH2SiMe3)2(R,R-bpzmm)(μ-OAr)] (6), is one of the first examples of a zinc complex capable of exerting a significant influence on the degree of enantioselectivity, with enriched-isotactic PLAs (Pi = 0.74) produced through an enantiomorphic site control mechanism.
- C - Artículos de Revista