A Stable Dialkylphosphinyl Radical

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• 作者：Shintaro Ishida ; Fumiya Hirakawa ; Takeaki Iwamoto
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：August 24, 2011
• 年：2011
• 卷：133
• 期：33
• 页码：12968-12971
• 全文大小：760K
• 年卷期：v.133,no.33(August 24, 2011)
• ISSN：1520-5126

文摘

Dialkylphosphinyl radical 1 was synthesized as thermally stable yellow crystals and found to be monomeric both in solution and in the solid state. EPR spectrum showed that the spin density of 1 is mainly localized on the 3p orbital of the dicoordinated phosphorus atom. A distinct absorption band due to the electronic transition from nonbonding electron pair orbital to singly occupied 3p orbital on the phosphorus atom of 1 was observed at 445 nm in solution. Phosphinyl radical 1 underwent facile reaction with carbon tetrachloride, hydrogen abstraction, and a unique reaction with a persistent radical, galvinoxyl, giving a cyclic phosphaalkene and a silylether.