Thiocarbonyl Pseudohalides - The Curious Case of Thiocarbonyl Dithiocyanate

Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn-anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X-ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kinetic reaction products by a lower transition states opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof-of-principle study we show that it in turn can be used for the complexation of nickel to yield (4).