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The bisketene radical cation and its formation by oxidative ring-Opening of cyclobutenedione

Université de Fribourg

  • Piech, Krzysztof Department of Chemistry, University of Fribourg, CH-1700 Fribourg, Switzerland
  • Bally, Thomas Department of Chemistry, University of Fribourg, CH-1700 Fribourg, Switzerland
  • Allen, Annette D. Department of Chemistry, University of Toronto, Canada
  • Tidwell, Thomas T. Department of Chemistry, University of Toronto, Canada
    05.03.2013
Published in:
  • The Journal of Organic Chemistry. - 2013, vol. 78, no. 7, p. 2908–2913
English Parent cyclobutenedione 1 was photolyzed and ionized in an Ar matrix at 10K. The bisketene 2 that results in both cases (in the form of its radical cation after ionization) was characterized by its IR spectrum and by high-level quantum chemical calculations. Experiment and theory show that the neutral bisketene has only a single conformation where the two ketene moieties are nearly perpendicular, whereas the radical cation is present in two stable planar conformations. The mechanism of the ring-opening reaction, both in the neutral and in the radical cation, is discussed on the basis of calculations. In the latter case it is a nonsynchronous process that involves an avoided crossing of states.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
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https://sonar.ch/global/documents/302883
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