Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1259 - 1266 (1988)
Update date:2022-08-25
Topics:
Logan, S. R.
Welsh, Michael R.
The dissociation of ferricenium tri-iodide in benzene solution has been studied by a photochemical technique under conditions where the concentration of the ion pair is many times greater than the equilibrium value.Kinetically the reaction is found to be of ca. three-halves order, with variations towards first-order or towards second-order behaviour, depending on the concentrations of iodine and ferrocene.The Arrhenius activation energy lies in the range 95-125 kJ mol-1, showing lower values at low concentrations.More rapid dissociation is found for phenylferroceneand slower reaction for 1,1'-diphenyl-, methyl- and 1,1'-dimethyl-ferrocene and for <3>ferrocenophane.A mechanism has been proposed which involves the intermediates Fn+I4-, Fn+I2-, and Fn+I-, and it is suggested that the variations in reaction order are a consequence of the variable importance of the reverse process of some of these reaction steps.
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