己内酯
化学
聚合
苯甲醇
催化作用
开环聚合
高分子化学
药物化学
立体化学
有机化学
聚合物
作者
Prasanna Kumar Ganta,Chia-Hsiung Chang,Hsing-Yin Chen,Rajiv Kamaraj,Sambandam Anandan,Yi‐Chun Lai,Yen-Chang Chu,Chen Yu Li,Chen Yu Li
出处
期刊:Organometallics
[American Chemical Society]
日期:2023-08-31
卷期号:42 (19): 2856-2866
被引量:2
标识
DOI:10.1021/acs.organomet.3c00317
摘要
A series of Al catalysts with N,N′-diaryloxalamidate and N,N′-diaryldithiooxalamidate ligands were synthesized, and their ε-caprolactone polymerization rates were determined in this study. Of the Al complexes bearing N,N′-diaryldithiooxalamidate, [PhHNCS]2Al2Me4 exhibited the highest catalytic activity (conv. of poly-ε-caprolactone = 94%; [ε-caprolactone]:[[PhHNCS]2Al2Me4]:[benzyl alcohol] = 100:0.5:2 with [ε-caprolactone] = 2 M at 25 °C after 20 min), and of the Al complexes bearing N,N′-diaryldioxalamidate, [PhHNCO]2Al2Me4 exhibited the highest catalytic activity (conv. of poly-ε-caprolactone = 94%; [ε-caprolactone]:[OHAl2Me4]:[benzyl alcohol] = 100:0.5:2 with [ε-caprolactone] = 2 M at 25 °C after 30 min). The Al complexes bearing N,N′-diaryldithiooxalamidate demonstrated a greater catalytic activity (1.4–7.3-fold) than Al complexes bearing N,N′-diaryldioxalamidate. Density functional theory calculations revealed that [PhiPrNCS]2Al2(OMe)4 with a weaker Al–OMe bond and less repulsion of the highest transition state TS1 revealed the lower potential energy of TS1 compared to [PhiPrNCO]2Al2(OMe)4 and further exhibited a higher polymerization rate than [PhiPrNCO]2Al2(OMe)4.
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