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Protonation of Malononitrile in Superacidic Solutions
Author(s) -
Schickinger Manuel,
Morgenstern Yvonne,
Stierstorfer Karin,
Kornath Andreas
Publication year - 2017
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.201700220
Subject(s) - malononitrile , protonation , chemistry , monoclinic crystal system , infrared spectroscopy , salt (chemistry) , deuterium , crystal structure , inorganic chemistry , medicinal chemistry , crystallography , organic chemistry , ion , physics , quantum mechanics , catalysis
Malononitrile reacts in superacidic solutions HF/ M F 5 ( M = As, Sb) with formation of the corresponding salts [H 2 C(CN X ) 2 ][ M F 6 ] 2 ( M = As, Sb; X = H, D). The occurrence of double protonation is strongly dependent on the stoichiometric ratio of the Lewis acid with regard to malononitrile. Deuterated species were obtained by replacing hydrogen fluoride with deuterium fluoride. The double protonated salts were characterized by vibrational spectroscopy and in the case of [H 2 C(CNH) 2 ][AsF 6 ] 2 · HF ( 3 ) by a single‐crystal X‐ray structure analysis. The salt crystallizes in the monoclinic space group P 2 1 / c with four formula units per unit cell. The vibrational spectra were compared to quantum chemical calculations of the free cation [(CN)H 2 C(CNH)] + .