Journal of the Chemical Society - Faraday Transactions p. 3603 - 3606 (1990)
Update date:2022-08-03
Topics:
Fisher, Adrian C.
Coles, Barry A.
Compton, Richard G.
Bethell, Donald
Tripathi, Sadhana
The oxidation of tris-(p-tolyl)amine (A) has been studied in acetonitrile solution using a channel electrode flow cell.In the dark a simple reversible one-electron oxidation to the corresponding (stable) radical cation is observed.However on irradiation with light of wavelength 300 nm a 'pre-wave' is additionally seen ca. 200 mV cathodic of the simple 'dark' process.Action spectrum measurements, preparative experiments and photocurrent/solution flow rate data are used to show that this process has the kinetic characteristics of a 'photo-CE' reaction in which the product of a photochemical pre-equilibrium involving A undergoes a dispropo rtionation reaction forming an electroactive species.The nature of the species involved is deduced and a detailed mechanistic scheme presented.Rate and equilibrium constants are estimated.The 'photo-CE' reaction is shown to have the unusual property for an electrode reaction at a channel electrode that the photocurrents decrease with solution flow rate.
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