Ultrafast carbene-carbene isomerization.
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.
Wang
Jin
J
Department of Chemistry, Ohio State University, Columbus, Ohio 43210, USA.
Burdzinski
Gotard
G
Kubicki
Jacek
J
Gustafson
Terry L
TL
Platz
Matthew S
MS