Radical Addition of Isolable Silyl Radicals for Open-Shell Functional Materials

一个持久的三（甲硅烷基）甲硅烷基自由基，双（三异丙基甲硅烷基）[苯基（二异丙基）甲硅烷基]甲硅烷基自由基是通过用钠还原相应的氟硅烷产生的。根据EPR谱，自旋不仅在不饱和硅上离域，而且在苯基上离域，成功地合成了一种可分离的二烷基氧膦基自由基，为黄色结晶固体，在溶液和固体中均为单体。氧膦基自由基的自旋密度几乎位于双配位磷原子的3p轨道上。在445 nm处，观察到氧膦自由基磷原子上的非键电子对轨道到单占据3p轨道的电子跃迁。由此获得的氧膦基自由基的反应性进行了研究。

A persistent tri(silyl)silyl radical, bis(triisopropylsilyl)[phenyl(diisopropyl)silyl]silyl radical was generated by the reduction of the corresponding fluorosilane with sodium. According to EPR spectroscopy, spin delocalized on not only unsaturated silicon but also phenyl group.An isolable diakylphosphinyl radical was successfully synthesized as a yellow crystalline solid and found to be monomeric both in solution and in the solid state. The spin density of the phosphinyl radical is almost localized on the 3p orbital of the dicoordinated phosphorus atom. Distinct electronic transition from nonbonding electron pair orbital to singly occupied 3p orbital on the phosphorus atom of the isolated phosphinyl radical was observed at 445 nm in solution. The reactivity of thus obtained phosphinyl radical has been investigated.