A Stable Dialkylphosphinyl Radical

作者:Ishida Shintaro*; Hirakawa Fumiya; Iwamoto Takeaki
来源:Journal of the American Chemical Society, 2011, 133(33): 12968-12971.
DOI:10.1021/ja205001m

摘要

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.

  • 出版日期2011-8-24