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Halogenated Carboxonium Salts: Preparation and Structural Analysis.

Rolf Minkwitz1, Stefan Reinemann, Oliver Blecher

  • 1Anorganische Chemie, Fachbereich Chemie der Universität Dortmund, D-44221 Dortmund, Germany, and Institut für Anorganische und Analytische Chemie der Freien Universität Berlin, D-14195 Berlin, Germany.

Inorganic Chemistry
|October 24, 2001
PubMed
Summary
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Dalton transactions (Cambridge, England : 2003)·2018

Researchers synthesized and isolated halogenated alkylidene oxonium salts. These compounds were characterized using spectroscopy and X-ray crystallography, revealing distinct structural features for chlorine and fluorine variants.

Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Solid-State Chemistry

Background:

  • Alkylidene oxonium salts are reactive intermediates with applications in synthesis.
  • Understanding their preparation and structural properties is crucial for further chemical exploration.

Purpose of the Study:

  • To investigate the synthesis and isolation of novel halogenated alkylidene oxonium salts.
  • To characterize these salts using spectroscopic and crystallographic methods.
  • To elucidate the structural differences between chlorine and fluorine substituted analogues.

Main Methods:

  • Reaction of dichloromethylmethylether with superacidic media (HF/MF(5)) at low temperatures.
  • Characterization using low-temperature Infrared (IR) and Raman spectroscopy.

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  • X-ray crystallography for determining the crystal structures of hexafluoroantimonate salts.

    • Main Results:

    • Successful synthesis of chlorine (CH(3)OCHCl(+)MF(6)(-)) and fluorine (CH(3)OCHF(+)MF(6)(-)) substituted oxonium salts.
    • Identification of a chlorine/fluorine exchange reaction at different temperatures.
    • Determination of the crystal structures for CH(3)OCHF(+)SbF(6)(-) and CH(3)OCHCl(+)SbF(6)(-), revealing differences in cation structures and crystallizing in monoclinic space group P2(1)/c.

    Conclusions:

    • The study successfully prepared and isolated halogenated alkylidene oxonium salts.
    • Spectroscopic and crystallographic data provide detailed insights into their structures.
    • The findings highlight the influence of halogen substitution on the structural characteristics of these oxonium salts.