Conclusions
Consideration of the foregoing results leads us to the following generalizations. The molecular wave functions of the mobile electrons are not localized on individual groups of atoms in the compounds under consideration, but belong to the molecule as a whole. The fact that the oxygen atom is linked to two unsaturated radicals leads to a considerable additional change in the density of the mobile electrons of this atom. The interaction of the p electrons of oxygen with each of these radicals, as expressed in the density distribution of the mobile electrons, is primarily determined by the nature of the particular radical, and apparently to a lesser extent by the nature of the second radical.
An increase in the acceptor properties of one of the radicals leads to an increase in the calculated positive charge on the oxygen atom and in the order of the corresponding C−O bond. Changes in the order of the second C−O bond and the density distribution of the mobile electrons neighboring this bond are determined by weak composition for the p electron of the oxygen between the unsaturated groups to which this atom is attached.
We may suppose that the change in the integral Raman-line intensity associated with the valence vibrations of the double bond and, possibly, the oscillations of the benzene-ring framework (∼1600 cm−1) in vinylaryl ethers is connected with the existence of a common system of mobile electrons and with variations in the polarizability of this system.
The author finds it his pleasant duty to express sincere thanks to Professor N. A. Prilezhaeva of Tomsk University for help and valuable discussions.
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Translated from Zhurnal Strukturnoi Khimii, Vol. 7, No. 3, pp. 417–427, May–June, 1966
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Frolov, Y.L. Physical studies in the field of unsaturated aryl ethers and their derivatives. J Struct Chem 7, 393–402 (1966). https://doi.org/10.1007/BF00744431
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DOI: https://doi.org/10.1007/BF00744431