A comparative study of titanium complexes bearing 2-(arylideneamino)phenolates and 2-((arylimino)methyl)phenolates as catalysts for ring-opening polymerization of ϵ-caprolactone and l-lactide

Ling Jo Wu, Ravi Kumar Kottalanka, Yu Ting Chu, Zheng Ian Lin, Chun Juei Chang, Shangwu Ding, Hsuan Ying Chen, Kuo Hui Wu, Chih Kuang Chen

研究成果: 雜誌貢獻期刊論文同行評審

摘要

Titanium complexes bearing 2-(arylideneamino)phenolates and 2-((arylimino)methyl)phenolates were synthesized, and their catalytic activities in the polymerization of ϵ-caprolactone and l-lactide were studied. Among five-membered ring Ti complexes bearing 2-(arylideneamino)phenolates, FCl-Ti exhibited the highest level of catalytic activity ([CL] : [FCl-Ti] = 100 : 1, where [CL] = 2 M, and conv. = 86% at 60 °C after 9 h). For six-membered ring Ti complexes bearing 2-((arylimino)methyl)phenolates, SCl-Ti exhibited the highest level of catalytic activity ([CL] : [SCl-Ti] = 100 : 1, where [CL] = 2 M, and conv. = 88% at 60 °C after 118 h). The five-membered ring Ti complexes bearing 2-(arylideneamino)phenolates exhibited a higher level of catalytic activity (6.1-12.8 fold for the polymerization of ϵ-caprolactone and 6.2-23.0 fold for the polymerization of l-lactide) than the six-membered ring Ti complexes bearing 2-((arylimino)methyl)phenolates. The density functional theory (DFT) results revealed that the free energy of the first transition state FH-Ti-TS1 is 36.49 kcal mol−1 which is lower than that of SH-Ti-TS1 (46.58 kcal mol−1), which was ascribed to the fact that the Ti-Nim bond (2.742 Å) of FH-Ti-TS1 is longer than that of SH-Ti-TS1 (2.229 Å) and reduces the repulsion between ligands.

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頁(從 - 到)15660-15673
頁數14
期刊Dalton Transactions
53
發行號37
DOIs
出版狀態已出版 - 28 8月 2024

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