Modification of water-soluble oxidants

2[MH(OEP)] + 2TEMPO [M2(OEP)2] + 2TEMPOH 8.9 Modification of water-soluble oxidants 

The modification of potassium permanganate, KMnQi, has been carried out in the same manner. Althou this reagpnt is commonly used as an oxidant in aqueous solutions,220 a serious disadvantage that accompanies its use is its thermodynamic instability in aqueous media, Eq. 8.63  

The modification of water-soluble perruthenate salts into more hydrophobic analogs has been desCTibed.226 in non-aqueous media, salts of [Ru04h such as [( -Bu)4N][Ru04],227 [(M-Pr)4N][Ru04],228 [Ph4P][Ru04], and [PPN][Ru04p29 are remarkably mild oxidants. Stoichiometric oxidation of primary alcohols to aldehydes and secondary alcohols to ketones without 

The modification of the traditional oxidant, K3[Fe(QJ)6L has been reported by Masdrarak o who prepared the hydrophobic analog, [Et4N]3lFe(a )6]- Cyclic voltammetry showed a regular shift in E /2 to more positive values upon gradual addition of a more-polar solvent to a less-polar one. Table 8.4  

Although [Et4N]3[Fe(CN)6] has been desaibed as a mild oxidant230 in organic solvents, the potential can be shifted to more positive values by addition of water or methanol, thus indicating the possibility of use as a tunaUe oxidant . Indeed, [Et4N][Fe(SPh)4] is staHe in acetonitrile in the presence of [Et4N]3[Fe CN)6l but is converted into [Fe(SPh)4h upon addition of water (6%). 

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