ELECTRON TRANSFER REACTIONS OF THIOSULFATE ION AND DIAQUOTETRAKIS (2,2’- BIPYRIDINE) - µ - OXO......

The electron transfer interactions of thiosulfate ions and diaquotetrakis (2,2'- bipyridine) - - oxodiruthenium(III) ion, [(H2O)2(bpy)4Ru2O]4+, have been examined in perchloric acid at T = 31.0 1°C, ionic strength, I = 0.5 mol dm-3 (NaClO4), and The reaction has a 1:2 stoichiometry ([(H2O)2(bpy)4Ru2O]4+: S2O32–], first order dependence on [(H2O)2(bpy)4Ru2O]4+] and [S2O32–], second order overall). Increases in [H+] had a direct effect on reaction rates, but increases in ionic strength had a negative effect on reaction rates. –d[[(H2O)2Ru2O4+]/ dt = (a+b[H+]) has been offered as the rate equation for the reaction. [[(H2O)2Ru2O4+] [S2O32–]. The speeds of the reaction were changed by adding anions and cations. It is proposed that the reaction most likely proceeded through the outer sphere mechanism, based on the lack of evidence of the formation of intermediate complex (absence of intercept in the Michaelis-Menten plot and lack of shift in the max of the reaction mixture 1 minute after start of reaction from that of the dimer) and observable added ion catalysis. The author proposes a feasible mechanism.

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