title: Generation of triarylamine radical cations through reaction of triarylamines with Cu(II) in acetonitrile. A kinetic investigation of the electron-transfer reaction.
abstract: Triphenylamine derivatives react with Cu(2+) 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 x 10(2) to 2.15 x 10(5) 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 H(el) provided a good fit with H(el) = 100 cm(-1) suggesting that electron transfer in the TPA/Cu(2+) 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.
authors.affiliation: Photosciences and Photonics, Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology, Council of Scientific and Industrial Research, Trivandrum 695 019, India.
authors.forename: Kesavapillai
authors.initials: K
authors.lastname: Sreenath
authors.forename: Chettiyam Veettil
authors.initials: CV
authors.lastname: Suneesh
authors.forename: Karical R
authors.initials: KR
authors.lastname: Gopidas
authors.forename: Robert A
authors.initials: RA
authors.lastname: Flowers