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

一种持久的三(硅基)硅基自由基bis(triisopropylsilyl)[phenyl(diisopropyl)silyl]silyl自由基是由相应的氟硅烷与钠还原生成的。根据EPR谱，自旋不仅在不饱和的硅上发生离域，而且在苯基上也发生离域。以黄色结晶固体的形式成功地合成了可分离的二烷基膦自由基，发现它在溶液和固体中都是单体。膦自由基的自旋密度几乎集中在双配位磷原子的3p轨道上。在溶液中，在445 nm处观察到了膦自由基磷原子上从非键电子对轨道到单占据3p轨道的明显的电子跃迁。研究了由此得到的膦自由基的反应活性。

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.