Triaryl-silyl, -germyl, and -stannyl radicals .MAr3 (M = Si, Ge, or Sn and Ar = 2,4,6-Me3C6H2) and .Ge(2,6-Me2C6H3)3: Synthesis and ESR studies
作者:Michael J.S. Gynane、Michael F. Lappert、Paul I. Riley、Piérre Rivière、Monique Rivière-Baudet
DOI:10.1016/s0022-328x(00)81378-9
日期:1980.12
have been prepared from the appropriate triarylmetal chloride, MAr3Cl, and an electron-rich olefin [R]2 (R = Me or Et) under UV irradiation in toluene at low temperature. The triarylgermyl radicals are persistent (t > 24 h, 20°C) whilst the analogous tin and silicon radicals are only stable under constant irradiation at temperatures below −20°C; the ESR spectra of the germanium radicals and of .Si(2
以三芳基金属为中心的自由基。MAr 3(M = Si,Ge或Sn; Ar = 2,6-Me 2 C 6 H 3或2,4,6-Me 3 C 6 H 2)已由适当的三芳基金属氯化物MAr 3 Cl制备,以及在低温下在甲苯中紫外线照射下的富电子烯烃[ R] 2(R = Me或Et)。三芳基锗烷基自由基具有持久性(t > 24 h,20°C),而类似的锡和硅自由基仅在低于-20°C的恒定辐射下稳定。锗自由基和锗的ESR谱。Si(2,4,6-Me 3C 6 H 2)3(它是第一个被光谱鉴定的三芳基甲硅烷基基团)显示出所有质子偶合的等价等效物,这是由于芳族环扭曲成围绕金属的“螺旋桨”排列所致。还报道了这些自由基的前体的合成和表征。