This work reports the efficient polymerization of 4-vinylpyridine (4VP) using Lewis pairs composed of homoleptic rare-earth (RE) aryloxides and ylide-functionalized phosphines (YPhos). The resultant P4VP was readily quaternized by the addition of 1-bromododecane. Polymerization of 4VP derivatives (2-methoxy-4-vinylpyridine, 4-vinylquinoline, and 2,6-dimethyl-4-vinylpyridine) also occurred under identical reaction conditions. The RE/YPhos Lewis pair polymerization system effectively copolymerized 4VP with methyl methacrylate, which resulted in copolymers with gradient architectures and narrow molecular weight distributions. A combined experimental and computational study provided critical insights into the polymerization mechanism. Density functional theory calculations also revealed that the use of YPhos as a Lewis base greatly facilitated both the initiation and subsequent monomer insertion in comparison with PEt₃.

中文翻译：

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用于4-乙烯基吡啶及其衍生物聚合的稀土芳基氧化物/叶立德官能化膦受阻路易斯对

这项工作报告了使用由均配稀土 (RE) 芳基氧化物和叶立德官能化膦 (YPhos) 组成的路易斯对有效聚合 4-乙烯基吡啶 (4VP)。通过添加 1-溴十二烷，所得的 P4VP 很容易季铵化。4VP 衍生物（2-甲氧基-4-乙烯基吡啶、4-乙烯基喹啉和2,6-二甲基-4-乙烯基吡啶）的聚合也在相同的反应条件下发生。RE/YPhos Lewis 对聚合系统有效地将 4VP 与甲基丙烯酸甲酯共​​聚，从而产生具有梯度结构和窄分子量分布的共聚物。结合实验和计算研究为聚合机制提供了重要的见解。₃ .