Photochemical reactions of 2-(pentamethyldisilanyl)furan and 2-(pentamethyldigermanyl)furan. Formation of a radical pair
作者:Kunio Mochida、Kohichi Kimijima、Masanobu Wakasa、Hisaharu Hayashi
DOI:10.1016/0022-328x(94)87043-8
日期:1994.2
Photochemical reactions of 2-(pentamethyldisilanyl)furan and 2-(pentamethyldigermanyl)furan have been investigated by chemical trapping experiments and laser flash-photolysis. On irradiation, the furylated catenates of Group 14 elements undergo silicon-silicon σ bond and germanium-germanium σ bond homolysis to give a pair of silyl radicals and germyl radicals, respectively. In CCl4, these radicals
通过化学捕获实验和激光闪光光解法研究了2-(五甲基二硅烷基)呋喃和2-(五甲基二硬脂基)呋喃的光化学反应。辐射时,第14组元素的糠基化链状酸酯均经历硅-硅σ键和锗-锗σ键均溶,分别得到一对甲硅烷基和胚芽自由基。在CCl 4中,这些自由基通过提取氯原子而转化为相应的氯化物。在非卤代溶剂(环己烷和其他烃类)中,甲硅烷基自由基发生歧化,以甲硅烷和甲硅烷为主要产物。三甲基锗烷基自由基主要在ipso上偶联成对基团的呋喃基的-位以产生相应的双自由基。该双自由基经历了二价物质二甲基亚锗烯的消除,同时形成了2-(三甲基锗烷基)呋喃。