1323976-90-4Relevant academic research and scientific papers
Redox Reactions of a Stable Dialkylphosphinyl Radical
Hirakawa, Fumiya,Ichikawa, Hitomi,Ishida, Shintaro,Iwamoto, Takeaki
, p. 2714 - 2716 (2015)
A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P?), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P? with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]- and [K(crypt-222)]+[RH2P]-. Whereas [K(18-c-6)]+[RH2P]- exists as a contact ion pair, [K(crypt-222)]+[RH2P]- exists as a solvent-separated ion pair in the solid state. Reaction of RH2P? with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).
A stable dialkylphosphinyl radical
Ishida, Shintaro,Hirakawa, Fumiya,Iwamoto, Takeaki
, p. 12968 - 12971 (2011)
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.
