Experimental and Theoretical Study of 2,6‐Difluorophenylnitrene, Its Radical Cation, and Their Rearrangement Products in Argon Matrices

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Abstract
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.

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