Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne‐containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1‐disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.

中文翻译：

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金催化CH官能化缩聚反应合成芳族聚合物。

均金（Au）络合物在现代有机化学中已显示出巨大的用途。然而，它们在聚合物合成中的应用仍然很少。本文中，我们证明了Au络合物在含炔共聚单体和杂芳基亲核试剂缩聚反应中的首次催化应用。聚合通过连续的分子间加氢芳基化反应发生，从而产生具有1,1-二取代烯烃主链键的高分子量芳族共聚物。基于催化剂的结构和抗衡离子配对，在聚合速率和聚合度（DP）之间建立了明确的相关性，从而使聚合反应能够以显着的效率，高反应性和出色的DP进行。反应性范围广，使高度官能化的芳族和脂族单体共聚。这些结果突出了Au催化在提供获得新的大分子构建体方面的未开发的效用。