Switching Off Electron Transfer Reactions in Confined Media: Reduction of [Co(dipic)<sub>2</sub>]<sup>−</sup> and [Co(edta)]<sup>−</sup> by Hexacyanoferrate(II)
2012-03-05T00:00:00Z (GMT) by
The kinetics of reduction of two cobalt(III) complexes with similar redox potentials by hexacyanoferrate(II) were investigated in water and in reverse micelle (RM) microemulsions. The RMs were composed of water, surfactant [(sodium(bis(2-ethylhexylsulfosuccinate)), NaAOT], and isooctane. Compared to the reaction in water, the reduction rates of (ethylenediaminetetraacetato)cobaltate(III) by hexacyanoferrate(II) were dramatically suppressed in RM microemulsions whereas a slight rate increase was observed for reduction of bis-(2,6-dipicolinato)cobaltate(III). For example, the ferrocyanide reduction of [Co(dipic)<sub>2</sub>]<sup>−</sup> increased from 55 M<sup>–1</sup> s<sup>–1</sup>in aqueous media to 85 M<sup>–1</sup> s<sup>–1</sup> in a <i>w</i><sub>o</sub> = 20 RM. The one-dimensional (1-D) and two-dimensional (2-D) <sup>1</sup>H NMR and FT-IR studies are consistent with the reduction rate constants of these two complexes being affected by their location within the RM. Since reduction of [Co(edta)]<sup>−</sup> is switched off, in contrast to [Co(dipic)<sub>2</sub>]<sup>−</sup>, these observations are attributed to the penetration of the [Co(edta)]<sup>−</sup> into the interfacial region of the RM whereas [Co(dipic)<sub>2</sub>]<sup>−</sup> is in a region highly accessible to the water pool and thus hexacyanoferrate(II). These results demonstrated that compartmentalization completely turns off a redox reaction in a dynamic microemulsion system by either reactant separation or alteration of the redox potentials of the reactants.