Isolable Diphosphorus-Centered Radical Anion and Diradical Dianion

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• 作者：Gengwen Tan ; Shuyu Li ; Sheng Chen ; Yunxia Sui ; Yue Zhao ; Xinping Wang
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：June 1, 2016
• 年：2016
• 卷：138
• 期：21
• 页码：6735-6738
• 全文大小：346K
• 年卷期：0
• ISSN：1520-5126

文摘

Two salts containing diphosphorus-centered radical anion 1^•– and diradical dianion 1^2–•• were obtained by one- and two-electron reductions of an indenofluorene-bridging diphosphaalkene (1) with K and KC₈, respectively. The salts have been characterized by electron paramagnetic resonance (EPR) spectroscopy, UV–vis absorption spectroscopy, and single-crystal X-ray diffraction analysis. EPR spectroscopy and theoretical calculations reveal that the spin density of the radicals mainly resides on the phosphorus atoms, and 1^2–•• has an open-shell singlet ground state. 1^•– and 1^2–•• represent the first isolable and structurally characterized diphosphorus-centered radical anion and dianion.