A laser flash photolysis study of 2-naphthyl(carbomethoxy)carbene

Authors
Wang, JL Likhotvorik, I Platz, MS
Citation
Jl. Wang et al., A laser flash photolysis study of 2-naphthyl(carbomethoxy)carbene, J AM CHEM S, 121(12), 1999, pp. 2883-2890
Citations number
56
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN journal
00027863 → ACNP
Volume
121
Issue
12
Year of publication
1999
Pages
2883 - 2890
Database
ISI
SICI code
0002-7863(19990331)121:12<2883:ALFPSO>2.0.ZU;2-7
Abstract
Photolysis of methyl 2-diazo(2-naphthyl)acetate releases singlet 2-naphthyl (carbomethoxy)carbene. The singlet carbene relaxes to the lower energy trip let state within 350 ps-1 ns. Singlet to triplet carbene intersystem crossi ng is much faster than Wolff rearrangement to the corresponding ketene. The barrier to Wolff rearrangement of the spin-equilibrated carbene is 3.4 kca l/mol in hexafluorobenzene. In this system, ketene is formed from the carbe ne and is not formed to a significant extent from an excited state of the d iazo compound.