Stable Tetraaryldiphosphine Radical Cation and Dication

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• 作者：Xiaobo Pan ; Yuanting Su ; Xiaoyu Chen ; Yue Zhao ; Yizhi Li ; Jinglin Zuo ; Xinping Wang
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：April 17, 2013
• 年：2013
• 卷：135
• 期：15
• 页码：5561-5564
• 全文大小：273K
• 年卷期：v.135,no.15(April 17, 2013)
• ISSN：1520-5126

文摘

Salts containing tetraaryldiphosphine radical cation 1^鈥? and dication 1²⁺ have been isolated and structurally characterized. Radical 1^鈥? has a relaxed pyramidal geometry, while dication 1²⁺ prefers a planar, olefin-like geometry with a two-electron 蟺 bond. The alteration of the geometries of the tetraaryldiphosphine upon oxidation is rationalized by the nature of the bonding. The EPR spectrum showed that the spin density of radical 1^鈥? is mainly localized on phosphorus atoms, which is supported by theoretical calculation.