KINETICS AND MECHANISM OF THE REACTION OF TRANS-CYCLOHEXANE-1,2-DIAMINE-NNN'N'-TETRA-ACETATOMANGANATE(III) WITH SUBSTITUTED THIOUREAS IN AQUEOUS-MEDIUM

The kinetics of reduction of [Mn(III)(cydta)]- (where H4cydta = trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5-4.5 and 9.2-10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the Mn(III) complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects.