Reaction of 1, 3-Dimethyl-2-Thiourea with Coordinated Superoxide in [(NH3)5 Co (µ-O2)Co(NH3)5]5+: A Mechanistic Study

Abstract

The reaction of 1, 3-dimethyl-2-thiourea with coordinated superoxide in [(NH3)5CO(µ-O2)CO(NH3)5]5+has been studied at 0.01 ≤ [H+] ≤ 0.16 mol dm-3 in aqueous perchloric acid medium under pseudo-first order conditions of an excess [DMTU] at µ = 0.25 mol dm-3 (NaClO4). The reaction is first order with respect to the oxidant and the reductant and is not hydrogen ion concentration dependent. Simple electron transfer is thought to have occurred leading to the oxygenation of the thiocarbamide. The products were analyzed using conventional methods. The reaction has been rationalized on the basis of the outer-sphere electron transfer mechanism.