Arns Rahel, McClish Rory, Hemberger Patrick, Bodi Andras, Bouwman Jordy, Kasper Tina, Schleier Domenik
Lehrstuhl Technische Thermodynamik, Fakultät für Maschinenbau, Universität Paderborn, Warburger Str. 100, 33098, Paderborn, Germany.
Department of Chemistry, University of Colorado, Boulder, Colorado, 80309, USA.
Angew Chem Int Ed Engl. 2025 Jul 28;64(31):e202503940. doi: 10.1002/anie.202503940. Epub 2025 Jun 17.
The incorporation of heteroatoms into the framework of polycyclic aromatic hydrocarbons (PAHs), in particular of nitrogen to yield polycyclic aromatic nitrogen heterocycles (PANHs), has been proposed for both astronomical and combustion environments, but no suitable precursors and pathways have been found. Analogous pathways to PAH formation are kinetically or energetically inhibited in the presence of a nitrogen heteroatom. We report on the reaction of phenylnitrene (PhN, c-CHN) with resonance-stabilized propargyl radicals (CH) and find that the association reaction bifurcates depending on the orientation of the attacking propargyl radical and yields multiple isomeric products. Among them, we identify the condensed-ring quinoline and conclude that nitrenes are viable candidates to drive the formation of PANHs.
将杂原子引入多环芳烃（PAHs）骨架，特别是引入氮以生成多环芳族氮杂环（PANHs），这在天文和燃烧环境中均已被提出，但尚未找到合适的前体和途径。在存在氮杂原子的情况下，与PAH形成类似的途径在动力学或能量上受到抑制。我们报道了苯炔（PhN，c-CHN）与共振稳定的炔丙基自由基（CH）的反应，发现该缔合反应根据进攻炔丙基自由基的方向而分叉，并产生多种异构体产物。其中，我们鉴定出稠环喹啉，并得出结论，氮烯是驱动PANHs形成的可行候选物。
