Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 75, Issue 19, Pages 6574-6580Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo1013405
Keywords
-
Categories
Funding
- Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2005/58320-4]
- Arbeitsgemeinschaft industrieller Forschungsvereinigungen (AiF)
- Deutscher Akademischer Austauschdienst (DAAD)
- Coordenadoria de Aperfeicoamento de Pessoal de Ensino Superior (CAPES) [BEX 1132/04-0]
Ask authors/readers for more resources
The activation parameters for the thermal decomposition of 13 acridinium-substituted 1,2-dioxetanes, bearing an aromatic moiety, were determined and their chemiluminescence emission quantum yields estimated, utilizing in situ photosensitized 1,2-dioxetane generation and observation of its thermal decomposition kinetics, without isolation of these highly unstable cyclic peroxides. Decomposition rate constants show linear free-energy correlation for electron-withdrawing substituents, with a Hammett reaction constant of rho = 1.3 +/- 0.1, indicating the occurrence of an intramolecular electron transfer from the acridinium moiety to the 1,2-dioxetane ring, as postulated by the intramolecular chemically initiated electron exchange luminescence (CIEEL) mechanism. Emission quantum yield behavior can also be rationalized on the basis of the intramolecular CIEEL mechanism, additionally evidencing its occurrence in this transformation. Both relations constitute the first experimental evidence for the occurrence of the postulated intramolecular electron transfer in the catalyzed and induced decomposition of properly substituted 1,2-dioxetanes.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available