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Z. Naturforsch. 2012,
67b, 1235 – 1240
doi:10.5560/ZNB.2012-0232
The Protonation of Dithiocarbamic Acid in Superacids HF/MF5: Synthesis and Characterization of H2NC(SH)2+ MF6− (M = As, Sb)
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, 81377 München, Germany
Reprint requests to Prof. Dr. Andreas Kornath. Fax: +49-89-2180-77867. E-mail:
andreas.kornath@cup.uni-muenchen.de
Received September 2, 2012 / published online November 30, 2012
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.
Key words: Dithiocarbamic Acid, Superacids, Vibrational Spectroscopy, NMR Spectroscopy, Protonation