Generation of triarylamine radical cations through reaction of triarylamines with Cu(II) in acetonitrile. A kinetic investigation of the electron-transfer reaction

Sreenath, Kesavapillai ; Suneesh, Chettiyam Veettil ; Gopidas, Karical R. ; Flowers, Robert A. (2009) Generation of triarylamine radical cations through reaction of triarylamines with Cu(II) in acetonitrile. A kinetic investigation of the electron-transfer reaction Journal of Physical Chemistry A, 113 (23). pp. 6477-6483. ISSN 1089-5639

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp9027222

Related URL: http://dx.doi.org/10.1021/jp9027222

Abstract

Triphenylamine derivatives react with Cu2+ in acetonitrile to give radical cations, which subsequently undergo dimerization to provide tetraphenylbenzidine derivatives. Kinetic aspects of radical cation formation were examined by stopped-flow spectrophotometry. A broad range of triphenylamine derivatives were studied, and the driving force for the electron-transfer reaction ranged from +3.67 to -8.56 kcal M-1 with rate constants varying from 1.09 × 102 to 2.15 × 105 M-1 s-1 for these systems. Reorganization energy for the electron-transfer reaction was estimated using experimentally determined activation parameters. Fitting of the rate data to the Marcus equation using different values of the electronic coupling matrix element Hel provided a good fit with Hel = 100 cm-1 suggesting that electron transfer in the TPA/Cu2+ system conforms to the Marcus-type electron transfer. Furthermore, the high reorganization obtained from these studies is consistent with significant bond cleavage in the transition state, and a mechanism consistent with the experimental data is proposed.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:62097
Deposited On:16 Sep 2011 04:37
Last Modified:16 Sep 2011 04:37

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