The Protonation of Dithiocarbamic Acid in Superacids HF/MF5: Synthesis and Characterization of H2NC(SH)2 + MF6 – (M = As, Sb)

Abstract

Dithiocarbamic acid reacts in the superacidic media HF/MF5 (M = As, Sb) under formation of the corresponding salts H2NC(SH)2 + MF6 -. The colorless compounds are stable in an inert gas atmosphere up to -20 °C. The salts have been characterized by NMR, IR and Raman spectroscopy. Reactions in DF/AsF5 were carried out to obtain D2NC(SD)2 + AsF6 - in order to confirm the assignments of the observed vibrational modes. Additionally, quantum-chemical calculations of the free cation, [A2NC(SA)2]+ (A=H, D), and of the [A2NC(SA)2(3HF)]+ unit on the PBE1BPE/6-311G(3df,3pd) level of theory are discussed.