Yang Wenbang, Zhang Li, Xiao Dengmengfei, Feng Rui, Wang Wenqing, Pan Sudip, Zhao Yue, Zhao Lili, Frenking Gernot, Wang Xinping
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, China.
Center of Materials Science and Engineering, Guangxi University of Science and Technology, Liuzhou, 545006, China.
Nat Commun. 2020 Jul 10;11(1):3441. doi: 10.1038/s41467-020-17303-4.
The concept of odd-electron σ-bond was first proposed by Linus Pauling. Species containing such a bond have been recognized as important intermediates encountered in many fields. A number of radicals with a one-electron or three-electron σ-bond have been isolated, however, no example of a diradical based odd-electron σ-bonds has been reported. So far all stable diradicals are based on two s/p-localized or π-delocalized unpaired electrons (radicals). Here, we report a dication diradical that is based on two Se∴Se three-electron σ-bonds. In contrast, the dication of sulfur analogue does not display diradical character but exhibits a closed-shell singlet.
奇电子σ键的概念最早由莱纳斯·鲍林提出。含有这种键的物种已被公认为是许多领域中重要的中间体。已经分离出了一些具有单电子或三电子σ键的自由基，然而，尚未有基于双自由基的奇电子σ键的例子被报道。到目前为止，所有稳定的双自由基都是基于两个s/p局域化或π离域化的未成对电子（自由基）。在此，我们报道了一种基于两个Se∴Se三电子σ键的双正离子双自由基。相比之下，硫类似物的双正离子不显示双自由基特征，而是表现为闭壳单重态。
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