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The Protonation of Acetamide and Thioacetamide in Superacidic Solutions: Crystal Structures of [H 3 CC(OH)NH 2 ] + AsF 6 – and [H 3 CC(SH)NH 2 ] + AsF 6 –
Author(s) -
Axhausen Joachim,
Ritter Cornelia,
Lux Karin,
Kornath Andreas
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200419
Subject(s) - chemistry , acetamide , monoclinic crystal system , crystallography , triclinic crystal system , protonation , crystal structure , hydrogen bond , tetramethylammonium , molecule , ion , organic chemistry
Acetamide and thioacetamide react with the superacid solutions HF/MF 5 (M = As, Sb) under formation of the corresponding salts [H 3 CC(OH)NH 2 ] + MF 6 – and [H 3 CC(SH)NH 2 ] + MF 6 – (M = As, Sb), respectively. The reaction of DF/AsF 5 with acetamide and thioacetamide lead to the corresponding deuterated salts [H 3 CC(OD)ND 2 ] + AsF 6 – and [H 3 CC(SD)ND 2 ] + AsF 6 – , respectively . The salts are characterized by vibrational and NMR spectroscopy, and in the case of [H 3 CC(OH)NH 2 ] + AsF 6 – and [H 3 CC(SH)NH 2 ] + AsF 6 – also by single‐crystal X‐ray analyses. The [H 3 CC(OH)NH 2 ] + AsF 6 – ( 1 ) salt crystallizes in the triclinic space group P $\bar{1}$ with two formula units per unit cell, and the [H 3 CC(SH)NH 2 ] + AsF 6 – ( 2 ) salt crystallizes in the monoclinic space group P 2 1 / c with four formula units per unit cell. In both crystal structures three‐dimensional networks are observed which are formed by intra‐ and intermolecular N–H ··· F and O–H ··· F or S–H ··· F hydrogen bonds, respectively. For the vibrational analyses, quantum chemically calculated spectra of the cations [H 3 CC(OH)NH 2 · 3HF] + and [H 3 CC(SH)NH 2 · 2HF] + are considered.