Kinetics and Mechanism of the Oxidation of Iodide by trans-Dioxoruthenium(VI)

Article abstract of DOI:10.1039/DT9940003091

The kinetics of reduction of trans-(2+) (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) by iodide has been studied in aqueous acidic solution.The reaction has the following stoichiometry: trans-(2+) + 3I(1-) + 2H(1+) --> trans-(2+) + I3(1-).The rate low is -d/dt = (k_a + k_b) with k_a = 0.041 +/- 0.013 dm³ mol^-1 s^-1 and k_b = 18.5 +/- 0.2 dm⁶ mol^-2 s^-2 at 25.0 deg C and 0.1 mol dm^-3 ionic strength.For k_a ΔH(excit.) = 42.9 +/- 9.4 kJ mol^-1 and ΔS(excit.) = -131 +/- 40 J K^-1 mol^-1, while for k_b, ΔH(excit.) = 36.9 +/- 2.9 kJ mol^-1 and ΔS(excit.) = -97 +/- 10 J K^-1 mol^-1.A mechanism involving oxygen-atom transfer from Ru(VI) to iodide is consistent with the data.

Full text of DOI:10.1039/DT9940003091

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

View Article Online