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The Protonation of Dimethyl Sulfoxide: Spectroscopic Examinations of [(CX 3 ) 2 SOX] + MF 6 − (X=H, D; M=As, Sb) and the X‐Ray Structure of [(CH 3 ) 2 SOH + ] 4 Ge 3 F 16 4−
Author(s) -
Hopfinger Mathias,
Lux Karin,
Kornath Andreas
Publication year - 2012
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201200037
Subject(s) - protonation , monoclinic crystal system , octahedron , chemistry , crystallography , crystal structure , molecule , dimethyl sulfoxide , infrared spectroscopy , salt (chemistry) , nuclear magnetic resonance spectroscopy , x ray crystallography , ion , stereochemistry , organic chemistry , diffraction , physics , optics
Dimethyl sulfoxide (DMSO) reacts with the superacidic solutions of XF/MF 5 and XF/GeF 4 (X=H, D; M=As, Sb) under formation of the corresponding salts [(CX 3 ) 2 SOX + ]MF 6 − and [(CH 3 ) 2 SOH + ] 4 Ge 3 F 16 4− , respectively. The salts are characterized by vibrational and NMR spectroscopy, and in the case of [(CH 3 ) 2 SOH + ] 4 Ge 3 F 16 4− also by single‐crystal X‐ray analysis. The salt [(CH 3 ) 2 SOH + ] 4 Ge 3 F 16 4− crystallizes in the monoclinic space group P 2 1 / c with two formula units in the unit cell. The crystal structure possesses an unusual anion consisting of a chain of three slightly distorted fluorine‐bridged GeF 6 octahedra. The vibrational spectra are compared to the quantum chemically calculated free [(CX 3 ) 2 SOX + ] cations. The described salts are isolated examples of completely protonated DMSO molecules in the condensed phase.