Collect. Czech. Chem. Commun. 2001, 66, 1038-1046

Are There Two Different Geometric Isomers of the O=C=N=C=O Cation?

František Tureček

Department of Chemistry, Bagley Hall, Box 351700, University of Washington, Seattle, WA 98195-1700, U.S.A.


Re-examination of the O=C=N=C=O+ cation reported previously by Eberlin et al. (J. Chem. Soc., Perkin Trans. 2 1997, 2347) yielded a single local minimum for the C2v bent structure (1a). The D∞h linear structure (1b) reported previously as a local minimum was found to be a second-order stationary point that, upon slight geometry perturbation, collapsed to a C2v transition state (1c) for degenerate inversion of the N-C-N angle in 1a. The ion enthalpy of formation was obtained from the enthalpies of three reactions as ∆Hf,298(1a) = 718 ± 6 kJ mol-1.

Keywords: Heterocumulenes; C2NO2 cation; Ion structure; Ion enthalpy of formation; Ab initio calculations; DFT; Mass spectrometry.

References: 24 live references.