Specific cation effect in the reaction of nitroprusside with cysteine, acetophenone and sulfite (Legal and Boedeker reaction).

The colour formation of cysteine (I), acetophenone (II) and sulfite (III) with the sodium and tetrabutylammonium (TBA) salt of nitroprusside (NP2-) in aqueous solution was studied. The intensity of colour formation depends strongly on the nature and concentration of the cations and increases in the order TBA less than Li less than Na less than K less than Rb less than Cs (in case of cysteine TBA and Li are interchanged). This specific cation effect was known for the Boedeker reaction (III) and is now also demonstrated for the Legal reaction (I and II). The adduct formation between NP2- and I to III is based on an anion-anion interaction. The role of the cation is to reduce the Coulombic repulsion between the reactants by ion-pair formation. The efficiency of ion-pair formation corresponds with the order given before except for TBA, which behaves divergently.