132361-36-5Relevant articles and documents
The Photo-CE Mechanism: the Oxidation of Tris-(p-tolyl)amine in Acetonitrile at an Illuminated Platinum Electrode
Fisher, Adrian C.,Coles, Barry A.,Compton, Richard G.,Bethell, Donald,Tripathi, Sadhana
, p. 3603 - 3606 (1990)
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.
