following CO photolysis from the parent molecule, is quickly solvated (<2 ps) via the CH bonds of the solvent. These species then rearranged to the silyl hydride product on a timescale of a few nanoseconds. These results were augmented by rearrangement studies in neat ethanol, propanol and hexanol solutions in which the initially formed metal CH complex rearranged to the metal hydroxyl complex. The mechanism
6 d 6组有机
金属化合物M(CO)5引起的SiH键活化反应的超快动力学(M = Cr,Mo和W)已经在环境条件下在纯三取代的
硅烷中进行了研究。使用飞秒泵浦-探针光谱法在紫外光解之后监测了CO拉伸带的超快光谱演变。发现由母体分子经CO光解后形成的配位不饱和物质通过溶剂的CH键迅速被溶剂化(<2 ps)。然后,这些物质在几纳秒的时间范围内重新排列为甲硅烷基氢化物产物。通过在纯乙醇,丙醇和己醇溶液中进行重排研究,可以增强这些结果,在这些溶液中,最初形成的金属CH络合物重排为
金属羟基络合物。通过将数据与文献中的各种模型进行比较,讨论了这种重排的机制。