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Synthesis and Structural Investigation of Protonated Haloacetyl Fluorides
Author(s) -
Steiner Sebastian,
Jessen Christoph,
Kornath Andreas J.
Publication year - 2022
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.202200060
Subject(s) - triclinic crystal system , monoclinic crystal system , chemistry , lone pair , crystallography , protonation , space group , fluoride , crystal structure , spectroscopy , fluorine , molecule , inorganic chemistry , x ray crystallography , diffraction , organic chemistry , ion , physics , optics , quantum mechanics
Herein, we report the O ‐monoprotonated species of chloroacetyl fluoride and fluoroacetyl fluoride in the binary superacidic systems HF/ M F 5 and DF/ M F 5 ( M =As, Sb) as hexafluoridoarsenates and hexafluoridostibates. The colorless salts were characterized by low temperature vibrational spectroscopy, low temperature NMR spectroscopy and single‐crystal X‐ray diffraction. [CClH 2 C(OH)F][SbF 6 ] crystallizes in the monoclinic space group P 2 1 /c with four formula units per unit cell and [CH 2 FC(OD)F][SbF 6 ] in the triclinic space group P 1 ‾ with two formula units per cell. The experimental data are discussed together with quantum chemical calculations at the ω B97XD/aug‐cc‐pVTZ‐level of theory. Protonation leads to significant shortening of the C−F bond due to back‐donation of fluorine lone‐pair electrons.