Kinetics of redox mediator tris(4-bromophenyl)amine in acetonitrile and ionic liquid [BMIm][PF6]: Oxidation of benzyl and cyclohexyl alcohols
- 作者：Ajith C. Herath ; James Y. Becker
- 关键词：Tris(4-bromophenyl)amine ; Catalytic current ; Apparent standard rate constant ; Ionic liquid
- 刊名：Journal of Electroanalytical Chemistry
- 出版年：2008
- 期刊代码：27_00220728
- 类别：ph
- 出版时间：15 July 2008
- 卷：619-620
- 期：Complete
- 页码：98-104
- 文件大小：312 K
摘要
A reversible one-electron oxidation of tris(4-bromophenyl)amine (TBPA) in acetonitrile or 1-butyl-3-methylimidazoliumhexafluorophosphate [BMIm][PF6] media unambiguously generates the cation-radical (TBPA
+), and its reduced form is catalytically regenerated in a follow-up chemical reaction with benzyl alcohol in the presence of 2,6-lutidine. The electron-transfer kinetics for these transformations has been investigated by a detailed comparison of the results obtained in both media. The apparent standard heterogeneous rate constant 
for an interfacial single-electron transfer of the mediator in acetonitrile containing 0.1 M Et4NClO4 was estimated using cyclic voltammetry (CV) profiles within a wide range of sweep rates (20–1000 mV s−1). The slightly higher 
value for the TBPA/TBPA+ couple at a Pt electrode surface was found to be (2.1 ± 0.8) 10−2 cm s−1 compared to (1.4 ± 0.6) 10−2 cm s−1 at a glassy carbon (GC) surface. 
values estimated in [BMIm][PF6] are comparatively two orders of magnitude lower (6.6 ± 0.5 × 10−4 cm s−1 and 4.9 ± 0.4 × 10−4 cm s−1 at Pt and GC, respectively). It has been found that the second-order homogeneous rate constant for the oxidation of benzyl alcohol by TBPA+ in acetonitrile (12.10 M−1 s−1) was estimated to be greater by one order of magnitude than that in ionic liquid [BMIm][PF6] (4.20 M−1 s−1). Similar experiments carried out for the oxidation of 2-chlorobenzyl alcohol, 4-tert-butylcyclo hexanol and 4-methylcyclohexanol by the TBPA+ showed no noticeable catalytic effect due to large potential difference of the mediator (Ep/2 = 0.74 V vs. Fc/Fc+), compared with those of the substrates.