Liu Shihua, Li Yinwu, Lin Jieli, Ke Zhuofeng, Grützmacher Hansjörg, Su Cheng-Yong, Li Zhongshu
LIFM, IGCME, School of Chemistry, Sun Yat-Sen University Guangzhou 510006 China
School of Materials Science and Engineering, Sun Yat-Sen University 510006 Guangzhou China.
Chem Sci. 2024 Mar 1;15(14):5376-5384. doi: 10.1039/d4sc00201f. eCollection 2024 Apr 3.
Distonic radical cations (DRCs) with spatially separated charge and radical sites are expected to show both radical and cationic reactivity at different sites within one molecule. However, such "dual" reactivity has rarely been observed in the condensed phase. Herein we report the isolation of crystalline 1λ,3λ-1-phosphonia-3-phosphinyl-cyclohex-4-enes 2a,b˙, which can be considered delocalized DRCs and were completely characterized by crystallographic, spectroscopic, and computational methods. These DRCs contain a radical and cationic site with seven and six valence electrons, respectively, which are both stabilized conjugation, yet remain spatially separated. They exhibit reactivity that differs from that of conventional radical cations (CRCs); specifically they show sequential radical and cationic reactivity at separated sites within one molecule in solution.
具有空间分离的电荷和自由基位点的双离子自由基阳离子（DRCs）有望在一个分子内的不同位点表现出自由基和阳离子反应性。然而，这种“双重”反应性在凝聚相中很少被观察到。在此，我们报告了结晶态的1λ,3λ-1-膦鎓-3-亚膦酰基-环己-4-烯2a,b˙的分离，其可被视为离域的双离子自由基阳离子，并通过晶体学、光谱学和计算方法进行了全面表征。这些双离子自由基阳离子分别包含一个具有七个和六个价电子的自由基位点和阳离子位点，二者均通过共轭作用得以稳定，但仍保持空间分离。它们表现出与传统自由基阳离子（CRCs）不同的反应性；具体而言，它们在溶液中的一个分子内的分离位点处表现出相继的自由基和阳离子反应性。
