Wang Jin, Burdzinski Gotard, Kubicki Jacek, Gustafson Terry L, Platz Matthew S
Department of Chemistry, Ohio State University, Columbus, Ohio 43210, USA.
J Am Chem Soc. 2008 Apr 23;130(16):5418-9. doi: 10.1021/ja8002827. Epub 2008 Mar 26.
The photochemistry of two isomeric aryl diazo ketones was investigated by fs time-resolved UV-vis and IR spectroscopies. Both diazo ketone excited states decompose in less than 300 fs by multiple pathways. One pathway involves concerted Wolff rearrangement and nitrogen extrusion, most likely in the syn rotomer. In the anti rotomer of one isomer, oxygen migration proceeds in concert with nitrogen extrusion to form rearranged keto carbene. This rotomer excited state also decomposes to form unrearranged carbene, which isomerizes in 5 ps.
通过飞秒时间分辨紫外可见光谱和红外光谱研究了两种异构芳基重氮酮的光化学性质。两种重氮酮激发态均通过多种途径在不到300飞秒的时间内分解。一种途径涉及协同的沃尔夫重排和氮气挤出，最有可能发生在顺式旋转异构体中。在一种异构体的反式旋转异构体中，氧迁移与氮气挤出协同进行，形成重排的酮卡宾。这种旋转异构体激发态也分解形成未重排的卡宾，其在5皮秒内异构化。
