Anion-binding interactions in nature have enabled the development of organocatalytic transformations; however, even though ionic species act as intermediates or precursors in many polymerizations, these interactions are underappreciated in polymerization catalysis. Here we introduce a powerful anion-binding catalytic strategy for cationic polymerization. In our approach, selenocyclodiphosph(V)azanes were designed as bench-stable hydrogen-bond donors to reversibly activate dormant covalent bonds (C–X, X=Cl, carboxylate and phosphate), in turn to precisely control the equilibrium between dormant covalent precursors and active cationic species under mild conditions. Experimental and computational analysis of this catalytic system revealed the key role of non-covalent anion-binding interactions between the catalyst and substrates. The living and controlled nature of this strategy, coupled with its capability for recycling catalysts and addressing certain fundamental constraints, such as metal residue and rigorous reaction conditions, delivers a versatile and robust living cationic polymerization methodology for precision polymer synthesis.

自然界中的阴离子结合相互作用促进了有机催化转化的发展；然而，尽管离子物质在许多聚合反应中充当中间体或前体，但这些相互作用在聚合催化中被低估了。在这里，我们介绍了一种用于阳离子聚合的强大的阴离子结合催化策略。在我们的方法中，硒环二磷（V）氮烷被设计为台式稳定的氢键供体，以可逆地激活休眠共价键（C-X、X=Cl、羧酸盐和磷酸盐），进而精确控制休眠共价前体之间的平衡和温和条件下的活性阳离子物质。该催化系统的实验和计算分析揭示了催化剂和底物之间非共价阴离子结合相互作用的关键作用。