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Experimental and theoretical study of 2,6-difluorophenylnitrene, its radical cation, and their rearrangement products in argon matrices

  • Carra, Claudio Department of Chemistry, University of Fribourg, Switzerland - USRA, Houston, USA
  • Nussbaum, Rafael Department of Chemistry, University of Fribourg, Switzerland
  • Bally, Thomas Department of Chemistry, University of Fribourg, Switzerland
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  • ChemPhysChem. - 2006, vol. 7(6), no. 1268-1275
English 2,6-Difluorophenylnitrene was reinvestigated both experimentally, in Ar matrices at 10 K, and computationally, by DFT and CASSCF/CASPT2 calculations. Almost-pure samples of both neutral rearrangement products (the bicyclic azirine and the cyclic ketenimine) of a phenylnitrene were prepared and characterized for the first time. These samples were then subjected to X-irradiation in the presence of CH₂Cl₂ as an electron scavenger, which led to ionization of the neutral intermediates. Thereby, it was shown that only the phenylnitrene and the cyclic ketenimine yield stable radical cations, whereas the bicyclic azirine decays to both of these compounds on ionization. The cyclic ketenimine yields a novel aromatic azatropylium-type radical cation. The electronic structure of the title compound is discussed in detail, and its relation to those of the iso-π-electronic benzyl radical and phenylcarbene is traced.
Faculté des sciences et de médecine
Département de Chimie
  • English
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