Synthetic, structural, mechanistic, and computational studies on single-site beta-diketiminate tin(II) initiators for the polymerization of rac-lactide |
| |
Authors: | Dove Andrew P Gibson Vernon C Marshall Edward L Rzepa Henry S White Andrew J P Williams David J |
| |
Institution: | Department of Chemistry, Imperial College London, UK. |
| |
Abstract: | A family of tin(II) complexes supported by beta-diketiminate ligands has been investigated as initiators for the polymerization of rac-lactide. Kinetic studies reveal a first-order dependence on lactide], but with a significant induction period. Linear plots of M(n) versus conversion and M](o)/I](o) versus conversion, along with narrow molecular weight distributions (typically 1.07-1.10), are indicative of well-controlled, "living" polymerizations. Less sterically hindered derivatives promote faster propagation than their bulky analogues, in accord with a more accessible active site. Enhanced rates of polymerization are observed for ligands bearing halogenated N-aryl substituents, a consequence of the more Lewis acidic nature of the Sn(II) centers. All of the initiators exhibit a similar bias toward heterotactic polylactide, which is attributed to a chain-end control mechanism influenced predominantly by the presence of the Sn 5s(2) lone pair of electrons rather than the steric or electronic properties of the beta-diketiminate ligand. The tin(II) isopropyl-(S)-lactate complex, ((Me)BDI(DIPP))SnOCH(Me)COO(i)Pr (14), has been synthesized as a model compound for the propagating species by treatment of ((Me)BDI(DIPP))Sn(NMe(2)) with isopropyl-(S)-lactate. An X-ray structure determination showed that the lactate ligand forms a five-membered chelate ring with a weak donor bond from the carbonyl oxygen atom to the tin center. A B3LYP density functional computational study indicates that insertion of the first lactide monomer into the tin(II) alkoxide bond is facile, with the induction period arising from a slower insertion of the second (and possibly third and fourth) monomer units. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|