Quantum Electronics Laboratory, Faculty of Physics, Adam Mickiewicz University, 85 Umultowska, Poznan 61-614, Poland.
J Am Chem Soc. 2010 Feb 24;132(7):2126-7. doi: 10.1021/ja909687g.
The mechanism of 1,2-H migration process in photoexcited alkyl diazo esters was studied by femtosecond IR transient absorption spectroscopy and theoretical calculations. Two possible processes are discussed: rearrangement in the diazo excited state (RIES) and the intermediacy of singlet carbene species. In chloroform solvent ulrafast IR data show a subpicosecond rise of alkene species indicating the occurrence of the RIES process. Failure in carbene species detection is explained by their absence or very low quantum yield of formation.
通过飞秒红外瞬态吸收光谱和理论计算研究了光激发的烷基重氮酯中 1,2-H 迁移过程的机理。讨论了两种可能的过程：重氮激发态的重排（RIES）和单重态卡宾中间体。在氯仿溶剂中，超快红外数据显示烯烃物种在亚皮秒内上升，表明 RIES 过程的发生。未检测到卡宾物种，这可以解释为其不存在或形成的量子产率非常低。
