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Asymmetric nitrogen. 76. Quantum chemical study of geometry and configurational stability of ketenimines

  • Physical Chemistry
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Bulletin of the Russian Academy of Sciences, Division of chemical science Aims and scope

Abstract

MNDO calculations were carried out of the ground and transitional states of the planar inversion of the N atom for ketenimines containing σ (Me, NH2, OH, OMe, and F) and π (CH = O) acceptor N substituents as well as for C-amino- and C-formylketenimines. Configurationally stable N-amino-, N-alkoxy-, and N-fluoroketenimines (inversion barriers ∼27–45 kcal/mole) are of interest for further experimental stereochemical studies. The geometry of the ketenimine fragment is determined in general byn N-πCC* conjugation. Other orbital and Coulombic interactions affect C- and N-substituent orientation relative to this fragment.

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Authors
  1. G. V. Shustov
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  2. A. V. Kachanov
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  3. S. N. Denisenko
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  4. R. G. Kostyanovskii
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Additional information

For previous communication, see [1].

N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2572–2578, November, 1992.

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Shustov, G.V., Kachanov, A.V., Denisenko, S.N. et al. Asymmetric nitrogen. 76. Quantum chemical study of geometry and configurational stability of ketenimines. Russ Chem Bull 41, 2028–2033 (1992). https://doi.org/10.1007/BF00863368

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  • DOI: https://doi.org/10.1007/BF00863368

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