Oxidation of thiosulfate by manganese(III) and nickel(III) complexes: A kinetic and mechanistic investigation

Abstract

AbstractThe kinetics of the oxidation of thiosulfate ion by [Mn(Y)]− (H4Y = trans‐cyclohezane‐1,2‐dimine‐N,N,N′,N′‐tetraacetic acid) and [Ni(L1)]2+ (HL1 = 15‐amino‐3‐methyl‐4,7,10,13‐tetraazapentadec‐3‐en‐2‐one oxime) have been investigated at 20.0, 30.0, and 40.0°C in aqueous solution and found to follow the general rate law −d/dt [complex] = kox[S2O32−] [complex]. The large negative entropy (ΔS‡) of activation for the reactions and the results of Marcus calculation provide support for inner‐sphere mechanism to be operative. © 1995 John Wiley & Sons, Inc.