The anodic oxidation of thiocyanate ion dissolved as KSCN in dimethylsulphoxide

Investigations on Organo–Sulfur–Nitrogen Rings and the Thiocyanogen Polymer, (SCN)x

“…It can also be prepared by chemical or electrical oxidation of thiocyanates in melts or solution [2,3] or, in the solid state, by passing chlorine gas over alkali metal thiocyanates. [4] Though all of these routes probably involve forming (SCN) 2 at some stage, it should be noted that the method in reference [4] may give rise to material contaminated with NaCl, since the reported yield is 135 %.…”

A selective one-pot electrochemical thiocyanation of methoxybenzene (anisole)

“…The advantageous electrochemical oxidation (by a clean ''oxidizing agent'') was performed both in a two-phase system [5,7] and in non-aqueous solutions [8,9]. However, the suggested electrochemical product was different in both cases.…”

“…It was claimed that in acetonitrile [8] and DMSO [9] the electrochemical oxidation of SCN À affords the radical SCN Å that undergoes a rapid dimerization at the electrode surface to form thiocyanogen, (SCN) 2 , as the thiocyanating agent. Controlled-potential electrolysis (CPE) on Pt at À10°C (to stabilize the thiocyanogen) in the presence of phenol gave 4-thiocyanatophenol as the sole product.…”

Potentiostatic transients related to the electrolytic oxidation of KSCN and mixtures of NaSCN + KSCN melts on polycrystalline platinum

“…Hence, the potentiostatic current transients should involve at least two different processes competing to cover the electrode surface. One of the simplest ways to represent the electrochemical formation of the reaction products from the discharge of SCN-ions is by two reaction pathways, each one involving a series of reactions with the p~ticipation of polymeric units: The initial discharge of SCN-ion is associated with a relatively fast and reversible reaction, as is indicated by previous results obtained in various different systems [9,14]. The rates of the following stages, either (Ib) or (IIb) and (IIc), imply the formation of new solid phases on the electrode surfaces.…”

“…Both a' and b' increase with temperature. According to this model, the electroformation of the anodic layer implies two-dimensional polymer units, and the slope b' should be related both to AC*, the activation energy for the formation of a critical nucleus according to the expression: AC* = b'RT/N, Es (9) and to g*, the number of molecules at equilibrium when the critical nucleus condition is attained. g* is given approximately by: g * = b'RT/zFE,2…”