Mei Yanbo, He Xue-Yi, Li Jiancheng, Liu Mo, Liang Qiuming, Yang Chengbo, Liu Liu Leo
Department of Chemistry, College of Science, Southern University of Science and Technology, Shenzhen, China.
Department of Chemistry, School of Sciences, Great Bay University, Dongguan, China.
Nat Commun. 2025 Mar 8;16(1):2321. doi: 10.1038/s41467-025-57660-6.
The stabilization of reactive anionic main group species utilizing carbenes constitutes a burgeoning and scarcely explored field. Herein, we report the synthesis of an anionic triphosphorus [P]- unit, supported by two cyclic (alkyl)(amino)carbenes (CAACs) in the form of potassium salts. This anion features a planar W-shaped conjugated C-P-P-P-C framework, characterized by 5-center-6-electron π delocalization and an additional σ lone pair located on each of the three phosphorus atoms. Remarkably, this anion is not only strongly basic and nucleophilic but also reductive, positioning versatile functionalization of the [P] unit. This approach has advanced the isolation of unique carbene-supported cores, including [HP], [PNR], [PO] and [P], thus expanding the frontiers of phosphorus chemistry. Moreover, the addition of the two phosphorus fragments upon P-P bond cleavage of the [P] unit to the triple bond of diphenylacetylene for the synthesis of an extended conjugated system was described.
利用卡宾对反应性阴离子主族物种进行稳定化是一个新兴且鲜有人探索的领域。在此，我们报道了一种以钾盐形式存在的、由两个环状（烷基）（氨基）卡宾（CAAC）支撑的阴离子型三磷[P]单元的合成。该阴离子具有平面W形共轭C-P-P-P-C骨架，其特征在于5中心-6电子π离域以及位于三个磷原子上的额外σ孤对电子。值得注意的是，该阴离子不仅具有强碱性和亲核性，还具有还原性，这为[P]单元的多功能官能化奠定了基础。这种方法推动了包括[HP]、[PNR]、[PO]和[P]在内的独特卡宾支撑核的分离，从而拓展了磷化学的前沿领域。此外，还描述了在[P]单元的P-P键断裂时，将两个磷片段加成到二苯乙炔的三键上以合成扩展共轭体系的过程。
