Burdzinski Gotard T, Wang Jin, Gustafson Terry L, Platz Matthew S
Quantum Electronics Laboratory, Faculty of Physics, Adam Mickiewicz University, 85 Umultowska, Poznan 61-614, Poland.
J Am Chem Soc. 2008 Mar 26;130(12):3746-7. doi: 10.1021/ja711346z. Epub 2008 Mar 1.
Photoinduced Wolff rearrangements were studied by femtosecond time-resolved UV-vis and IR transient absorption spectroscopy. For BpCN2COCH3 in acetonitrile the IR data indicate the presence of at least two mechanisms of ketene formation. The first process is fast proceeding in either 1BpCN2COCH3*, or in a hot carbene, or in both species, while the second is slow proceeding through the intermediacy of a relaxed carbene. The slow time constant of the ketene formation dynamics obtained by ultrafast IR (700 ps) spectroscopy agrees with the relaxed carbene decay of 800 +/- 100 ps obtained by UV-vis absorption spectroscopy.
通过飞秒时间分辨紫外可见和红外瞬态吸收光谱研究了光诱导沃尔夫重排反应。对于乙腈中的BpCN2COCH3，红外数据表明至少存在两种生成乙烯酮的机制。第一个过程在1BpCN2COCH3*、热卡宾或这两种物种中快速进行，而第二个过程通过松弛卡宾中间体缓慢进行。通过超快红外（700皮秒）光谱获得的乙烯酮生成动力学的慢时间常数与通过紫外可见吸收光谱获得的800±100皮秒的松弛卡宾衰减一致。
