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

开壳功能材料中可分离甲硅烷基的自由基加成

• 批准号: 21750035
• 负责人: ISHIDA Shintaro
• 金额: $ 2.58万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Young Scientists (B)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21750035/
• 关键词: 合成化学; ラジカル; ナノ材料; 高周期典型元素; リン; ホスフィニルラジカル; ESR; 結晶構造解析; シリル基の転位; シリルラジカル; ラジカル付加反応; 機能性材料; シングレットビラジカル

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.

通过用钠还原相应的氟硅烷，产生持久的三（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。根据EPR光谱，自旋不仅在不饱和硅上离域，而且在苯基上离域。成功合成了可分离的二烷基次膦基自由基，为黄色结晶固体，并发现在溶液和固态下都是单体。氧膦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 处观察到从非键合电子对轨道到孤立的氧膦基磷原子上的单占据 3p 轨道的明显电子跃迁。研究了由此获得的氧膦基自由基的反应性。