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The Carbonyl Chlorine(I) Cation [ClCO]+
Eduard Bernhardt1, Helge Willner1, Friedhelm Aubke2
1Anorganische Chemie der Universität, Lotharstrasse 1, D-47048 Duisburg (Germany), Fax: (+49) 203-379-2231.
Angewandte Chemie (International Ed. in English)
|May 2, 2018
Summary
Researchers have identified the first carbonyl halogen cation, [ClCO]+, in condensed phases. This superelectrophilic ion was characterized using vibrational spectroscopy and stabilized by fluoroantimonate ions.
Area of Science:
- Inorganic Chemistry
- Physical Chemistry
- Spectroscopy
Background:
- Carbonyl halides are important chemical intermediates.
- Superelectrophilic species are highly reactive and challenging to isolate.
- Previous studies have not definitively characterized carbonyl halogen cations in condensed phases.
Purpose of the Study:
- To synthesize and characterize the first carbonyl halogen cation in the condensed phase.
- To unambiguously establish the structure and properties of the [ClCO]+ ion.
- To investigate the stabilization of reactive cations by fluoroantimonate anions.
Main Methods:
- Reaction of carbonyl dichloride (COCl2) with antimony pentafluoride (SbF5) at room temperature.
- Isolation of the resulting cation in a suspension.
- Complete and fully assigned vibrational spectroscopy (e.g., IR, Raman) for characterization.
Main Results:
- The superelectrophilic [ClCO]+ ion was successfully synthesized and stabilized.
- A complete, fully assigned vibrational spectrum confirmed the cation's existence and structure.
- The [ClCO]+ ion was found to be stabilized by oligomeric fluoroantimonate ions.
Conclusions:
- The first condensed-phase carbonyl halogen cation, [ClCO]+, has been unequivocally identified.
- Vibrational spectroscopy is a powerful tool for characterizing highly reactive cationic species.
- Oligomeric fluoroantimonate anions effectively stabilize superelectrophilic cations in solution.
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