Persilylated Phosphoranyl Radicals: The First Persistent Noncyclic Phosphoranyl Radicals
作者:Yves Berchadsky、Christiane Bernard-Henriet、Jean-Pierre Finet、Robert Lauricella、Sylvain R. A. Marque、Paul Tordo
DOI:10.1002/chem.200600299
日期:2006.9.18
Persistent noncyclic phosphoranyl radicals have been prepared and observed by electron paramagnetic resonance (EPR) for the first time. They were obtained by UV-photolysis of a solution containing a bis(trialkylsilyl) peroxide (R = Me, Et) and a tris(trialkylsilyl) phosphite (R = Me, Et, iPr). EPR parameters (a(P) approximately 100 mT) are typical of phosphoranyl radicals exhibiting a trigonal-bipyramidal
持久性非环状磷烷基已制备并首次通过电子顺磁共振(EPR)观察到。它们是通过对含有双(三烷基甲硅烷基)过氧化物(R = Me,Et)和亚磷酸三(三烷基甲硅烷基)亚磷酸酯(R = Me,Et,iPr)的溶液进行紫外光解而获得的。EPR参数(a(P)大约为100 mT)是典型的具有三角双锥体结构的磷烷基自由基,奇数电子位于赤道位置。拟一阶衰变的分析表明,这些磷烷基自由基通过在双(三烷基甲硅烷基)过氧化物上的S(H)2均质取代和三烷基甲硅烷基氧基的损失(α-断裂反应)而衰变。S(H)2和α-断裂反应都取决于烷基的空间体积,即烷基的体积较大,