Lactide as the Playmaker of the ROP Game: Theoretical and Experimental Investigation of Ring-Opening Polymerization of Lactide Initiated by Aminonaphtholate Zinc Complexes
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- 作者：Dawid Jędrzkiewicz ; Grażyna Adamus ; Michał Kwiecień ; Łukasz John ; Jolanta Ejfler
- 刊名：Inorganic Chemistry
- 出版年：2017
- 出版时间：February 6, 2017
- 年：2017
- 卷：56
- 期：3
- 页码：1349-1365
- 全文大小：1017K
- ISSN：1520-510X
文摘
A family of homo- and heteroleptic zinc complexes bearing aminonaphtholate ligands was synthesized and fully characterized. Using NMR spectroscopy and DFT calculation, bis-alkoxy-bridged complexes [LZn(μ-OR)]2 were confirmed to have dimeric structures in solution, analogous to those obtained via X-ray crystallography. Surprisingly, a detailed experimental and theoretical study of the catalytic activity of [LZn(μ-OR)]2 in the ring-opening polymerization (ROP) of lactides showed that although well-defined alkoxy dimers possess a single-site structural motif, the most active initiator is obtained during in situ alcoholysis of the alkylzinc precursor. These results indicate that rational ancillary and alkoxy ligand design that takes into account its mutual interaction on monomer coordination may be key to the synthesis of new high-performance ROP catalysts.