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.

持续的三（Silyl）甲硅烷基自由基Bis（三异丙基硅烷基）[苯基（二异丙基）silyl] silyl自由基是通过与钠相应的氟硅烷还原而产生的。根据EPR光谱法，不仅在不饱和硅和苯基基团上脱离了自旋。磷酸自由基的自旋密度几乎定位在双核磷原子的3p轨道上。从溶液中的445 nm处观察到了从非键电子对轨道轨道到单一占据的3p轨道的明显电子过渡。已经研究了这样获得的磷酸自由基的反应性。