Thiocyanogen (SCN) 2 and selenocyanogen (SeCN) 2, electrochemically generated by anodic oxidation of the corresponding pseudohalides, were used to study the thiocyanation and selenocyanation of unsaturated hydrocarbons in acetonitrile. In the aprotic medium, the ambident character of the SCN− ion was revealed, two isomeric products were formed in similar yields, the dithiocyanato product, and the α-thiocyanato β-isothiocyanato ...