This study explores a pioneering catalytic reaction to obtain functional polymers and valuable byproducts. Using RuCl₂(PPh₃)₃ as a catalyst activates the C–N and N–H bonds in aromatic diamines, when combined with 1,4-butynediol. This activation initiates de-ammonification polycondensation, resulting in aromatic polyamines with a pyrrolyl end group and ammonia as a byproduct. The ammonia generated during the polycondensation process can be captured in cold water. The generation of ammonia during polycondensation was confirmed by UV-vis spectroscopy using the Nessler's reagent method. Subsequently, the aromatic polyamines were further functionalised via polymer reactions with 1,4-butanesultone and butyl isocyanate in the NH group. This yielded products with pendant sodium N-butylsulfonate and N-butylamide groups, respectively. The former exhibited a single-ion conductivity. Potential reaction mechanisms involving Ru-catalysed N–H and C–N bond activation in AD, along with the formation of terminal pyrrolyl groups, were investigated using density functional theorycalculations and ²H NMR spectroscopy.

中文翻译：

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钌络合物催化的芳香族二胺缩聚反应


本研究探索了一种开创性的催化反应，以获得功能性聚合物和有价值的副产品。使用 RuCl₂（PPh₃）₃ 作为催化剂，当与 1,4-丁炔二醇结合时，可激活芳香族二胺中的 C-N 和 N-H 键。这种活化启动脱氨缩聚反应，产生具有吡咯酰基末端基团的芳香族多胺，副产物为氨。缩聚过程中产生的氨可以用冷水捕获。使用 Nessler 试剂方法通过紫外-可见光谱证实了缩聚过程中氨的产生。随后，芳香族多胺通过与 NH 组中的 1,4-丁烷磺内酯和异氰酸丁酯的聚合物反应进一步官能化。这分别产生了具有悬垂 N-丁基磺酸钠和 N-丁酰胺基团的产物。前者表现出单离子导电性。使用密度泛函理论计算和 ²H NMR 波谱研究了涉及 AD 中 Ru 催化的 N-H 和 C-N 键激活以及末端吡咯基形成的潜在反应机制。