Pawlak Marta, Drzeżdżon Joanna, Jarzembska Katarzyna N, Jacewicz Dagmara
Department of Environmental Technology, Faculty of Chemistry, University of Gdansk, Wita Stwosza 63, Gdansk 80-308, Poland.
Department of Chemistry, University of Warsaw, Żwirki i Wigury 101, Warsaw 02-089, Poland.
Inorg Chem. 2025 Mar 17;64(10):4844-4853. doi: 10.1021/acs.inorgchem.4c04516. Epub 2025 Mar 3.
Isocyanides, due to the divalent carbon atom present in their structure, are among the most reactive groups of compounds in organic chemistry. Unfortunately, although according to the literature they do not have acute toxicity, they have a very unpleasant odor that makes it difficult to collaborate with them. However, despite the properties mentioned, reactions of isocyanides often lead to a variety of functional materials. In this article, we present a modified method for obtaining isocyanide-based polymers that significantly reduce the release of their hazardous vapors into the environment. For the study, a series of nickel(II) metal ion complex compounds containing organic ligands (e.g., 2,2'-bipyridyl, 1,10-phenanthroline, and diglycolate anion) were synthesized and used as catalysts in the oligomerization reaction of cyclohexyl isocyanide. The obtained oligomers were subjected to quantitative and qualitative physicochemical analyses (FT-IR, MALDI-TOF-MS, TGA/DSC, and DSC), which confirmed their structure and thermal properties. Reaction yields ranged from moderate (8-52%) to extremely high (94%) for a single catalyst. The synthesized catalytic systems are new, previously undescribed isocyanide oligomerization catalysts, which successfully led to the synthesis of poly(cyclohexyl isocyanide) and allowed us to obtain materials that can be used to produce many useful polymeric materials.
异腈由于其结构中存在二价碳原子，是有机化学中反应活性最高的化合物基团之一。不幸的是，尽管根据文献记载它们没有急性毒性，但它们具有非常难闻的气味，这使得与它们合作变得困难。然而，尽管有上述特性，异腈的反应通常会产生各种功能材料。在本文中，我们提出了一种改进的方法来制备基于异腈的聚合物，该方法可显著减少其有害蒸气向环境中的释放。为了进行这项研究，合成了一系列含有有机配体（例如2,2'-联吡啶、1,10-菲咯啉和二乙醇酸根阴离子）的镍（II）金属离子络合物，并将其用作环己基异腈低聚反应的催化剂。对所得低聚物进行了定量和定性的物理化学分析（傅里叶变换红外光谱、基质辅助激光解吸电离飞行时间质谱、热重分析/差示扫描量热法和差示扫描量热法），证实了它们的结构和热性能。对于单一催化剂，反应产率从中等（8 - 52%）到极高（94%）不等。所合成的催化体系是新型的、以前未描述过的异腈低聚催化剂，它们成功地实现了聚（环己基异腈）的合成，并使我们能够获得可用于生产许多有用聚合物材料的物质。
