Thiocarbonyl Pseudohalides – The Curious Case of Thiocarbonyl Dithiocyanate

Abstract

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 kintetic reaction products by a lower transition stateas opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof‐ofprinciple study we show that it in turn can be used for the complexation of Ni2+ (4).