Elusive Antimony-Centered Radical Cations: Isolation, Characterization, Crystal Structures, and Reactivity Studies

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• 作者：Tao Li ; Houjia Wei ; Yong Fang ; Lei Wang ; Sheng Chen ; Dr. Zaichao Zhang ; Dr. Yue Zhao ; Dr. Gengwen Tan and Prof. Dr. Xinping Wang
• 刊名：Angewandte Chemie
• 出版年：2017
• 出版时间：January 9, 2017
• 年：2017
• 卷：129
• 期：2
• 页码：647-651
• 全文大小：786K
• ISSN：1521-3757

文摘

One-electron oxidation of the stibines Aryl₃Sb (1, Aryl=2,6-ⁱPr₂-4-OMe-C₆H₂; 2, Aryl=2,4,6-ⁱPr₃-C₆H₂) with AgSbF₆ and NaBAryl^F₄ (Aryl^F=3,5-(CF₃)₂C₆H₃) afforded the first structurally characterized examples of antimony-centered radical cations 1^.+[BAryl^F₄]⁻ and 2^.+[BAryl^F₄]⁻. Their molecular and electronic structures were investigated by single-crystal X-ray diffraction, electron paramagnetic resonance spectroscopy (EPR) and UV/Vis absorption spectroscopy, in conjunction with theoretical calculations. Moreover, their reactivity was investigated. The reaction of 2^.+[BAryl^F₄]⁻ and p-benzoquinone afforded a dinuclear antimony dication salt 3²⁺[BAryl^F₄]₂⁻, which was characterized by NMR spectroscopy and X-ray diffraction analysis. The formation of the dication 3²⁺ further confirms that the isolated stibine radical cations are antimony-centered.