Inverse electron transfer in peroxyoxalate chemiexcitation using easily reducible activators

Quimica nova

Ciscato, Luiz Francisco Monteiro Leite¹  Bartoloni, Fernando Heering¹  Augusto, Felipe Alberto¹  Baader, Wilhelm Josef¹ 

[1] Universidade de São Paulo, São Paulo, Brasil

关键词: chemiluminescence;    electron transfer;    organic peroxides.;   

DOI  :  10.1590/S0100-40422010001000010

学科分类：化学（综合）

来源: Sociedade Brasileira de Quimica

【 摘 要 】

Chemiluminescenceproperties of the peroxyoxalate reaction in the presence of activators bearingelectron withdrawing substituents were studied, to evaluate the possible occurrenceof an inverse electron transfer, from the peroxide intermediate to the activator,in its chemiexcitation step. Relative catalytic rate constants and singlet quantumyields were obtained for the peroxyoxalate reaction, using 9-chloro, 9,10-dichloro,9-cyano and 9,10-dicyanoanthracenes as activators. The linear free-energy correlationof the relative rate constants with the activators' reduction potentials andthe dependence of the quantum yields on the released energy confirm, for thefirst time, the occurrence of this inverse electron transfer.

【 授权许可】

CC BY