Conclusions
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1.
According to the calculations based on the CNDO/2 and PNDO, the radicals and cation-radicals of oximes retain a planar structure and are radicals of theσ type, in which the spin density is predominantly localized on the oxygen and nitrogen atoms, respectively.
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2.
An estimate of the nucleophilic centers in oximes (C=N,\(\mathop \_\limits^--- \ddot N--- , \_\ddot O---\)) disclosed that on the basis of the values of the LCAO coefficients in the UOO and the charge distribution (CNDO/ 2 calculation) is is difficult to make an unequivocal conclusion regarding the direction of electrophilic attack. The protonation of oximes is most favorable at the C=N bond and least favorable at the oxygen.
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Literature cited
I. P. Freeman, Chem. Rev.,73, 283 (1973).
R. F. Hadson, Angew. Chem.,85, 63 (1973).
L. V. Gurevich, G. V. Karachevtsev, V. N. Kondrat'ev, Yu. A. Lebedev, V. A. Medvedev, and V. K. Potapov, Rupture Energy of Chemical Bonds. Ionization Potentials and Electron Affinity [in Russian], Nauka (1974).
A. Dargelos and C. Sandorfy, J. Chem. Phys.,67, 3011 (1977).
A. A. Buchachenko and A. M. Vasserman, Stable Radicals [in Russian], Khimiya (1973), p. 201.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2610–2612, November, 1979.
The authors are indebted to O. Yu. Dolgunicheva for supplying the results of the non-empirical calculation of (Ia).
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Turs, V.É., Karelov, A.A., Lyapin, N.M. et al. Structure of one-electron oxidation products of oximes. Russ Chem Bull 28, 2425–2427 (1979). https://doi.org/10.1007/BF00951732
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DOI: https://doi.org/10.1007/BF00951732