State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.
University of Chinese Academy of Sciences, Changchun Branch, Changchun, 130022, China.
Angew Chem Int Ed Engl. 2017 Nov 13;56(46):14653-14657. doi: 10.1002/anie.201707601. Epub 2017 Oct 11.
Rare-earth metal complexes (Flu-CH -Py)Ln(CH SiMe ) (THF) (Ln=Sc(1), Lu(2), Tm(3), Y(4) and Gd(5)), upon the activation of [Ph C][B(C F ) ] and Al Bu , were employed to catalyze the polymerization of allene derivatives under mild conditions. The Gd, Y, Tm, Lu metal based precursors exhibited distinguished 2,3-selectivity (>99.9 %) for phenylallene (PA) polymerization, whereas the smallest Sc metal based precursor showed a moderate 2,3-selectivity. The activity increased with the central metal size following the trend of Gd(5)>Tm(4)>Y(3)>Lu(2)>Sc(1). Moreover, Gd(5) also realized the purely 2,3-selective polymerizations of polar or nonpolar allene derivatives, para-methylphenylallene, para-flourophenylallene and para-methoxyphenylallene, regardless of electron-donating or -withdrawing substituents. Owing to the highly regular backbones, these polymers (except PPA) were crystalline, thus being the first crystalline polymers based on allene derivatives.
稀土金属配合物（Flu-CH -Py）Ln（CH SiMe ）（THF）（Ln=Sc（1），Lu（2），Tm（3），Y（4）和 Gd（5）），在[Ph C][B（C F ） ]和 Al Bu 的激活下，被用于在温和条件下催化烯丙基衍生物的聚合。镝、钇、铥、镥金属基前体对苯丙基烯（PA）聚合表现出显著的 2,3-选择性（>99.9％），而最小的钪金属基前体则表现出中等的 2,3-选择性。活性随着中心金属尺寸的增加而增加，遵循 Gd（5）>Tm（4）>Y（3）>Lu（2）>Sc（1）的趋势。此外，Gd（5）还实现了极性或非极性烯丙基衍生物、对甲基苯丙基烯、对氟苯丙基烯和对甲氧基苯丙基烯的纯 2,3-选择性聚合，无论电子供体还是受体取代基。由于具有高度规整的骨架，这些聚合物（除 PPA 外）都是结晶的，因此是第一个基于烯丙基衍生物的结晶聚合物。
