Inverse electron transfer in peroxyoxalate chemiexcitation using easily reducible activators

Química Nova

Ciscato, Luiz Francisco Monteiro Leite¹  Bartoloni, Fernando Heering¹  Augusto, Felipe Alberto¹  Universidade de São Paulo, São Paulo, Brasil¹  Baader, Wilhelm Josef¹ 

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 】

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

【 授权许可】

Unknown