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A Room-Temperature Stable Distonic Radical Cation |
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| Authors: | Prof Dr Xiaodan Chen Prof Dr Liu Leo Liu Shihua Liu Prof Dr Hansjörg Grützmacher Prof Dr Zhongshu Li |
| Institution: | 1. College of Chemistry and Materials Science, Jinan University, Guangzhou, 510632 China
These authors contributed equally to this work.;2. Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055 China;3. Lehn Institute of Functional Materials (LIFM), School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275 China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 30071 China;4. Lehn Institute of Functional Materials (LIFM), School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275 China |
| Abstract: | Distonic radical cations (DRCs) with spatially separated charge and radical sites have, so far, largely been observed by gas-phase mass spectrometry and/or matrix isolation spectroscopy work. Herein, we disclose the isolation of a crystalline dicarbondiphosphide-based β-distonic radical cation salt 3.+ (BARF) (BARF=B(3,5-(CF3)2C6H3)4)]−) stable at room temperature and formed by a one-electron-oxidation-induced intramolecular skeletal rearrangement reaction. Such a species has been validated by electron paramagnetic resonance (EPR) spectroscopy, single-crystal X-ray diffraction, UV/Vis spectroscopy and density functional theory (DFT) calculations. Compound 3.+ (BARF) exhibits a large majority of spin density at a two-coordinate phosphorus atom (0.74 a.u.) and a cationic charge located predominantly at the four-coordinate phosphorus atom (1.53 a.u.), which are separated by one carbon atom. This species represents an isolable entity of a phosphorus radical cation that is the closest to a genuine phosphorus DRC to date. |
| Keywords: | carbenes dicarbondiphosphide distonic radical cations phosphorus radicals |