Abstract
The paper is devoted to the investigation of the trans-effect of a heteroatom Z in substituted alkanes and alkenes revealing itself as non-equivalence of the cis- and trans-arranged Cβ–Cγ (or Cβ–H) bonds with respect to the Z–Cα bond. To this end, we invoke the power series for the bond order matrix obtained previously in terms of submatrices describing the direct (through-space) and indirect (through-bond) interorbital interactions (V. Gineityte, J. Mol. Struct. (Theochem) 343 (1995) 183; 364 (1996) 85; 434 (1998) 43). The expressions for the third order corrections to occupation numbers are additionally derived that are absent in the previous contributions but necessary for the investigation of the trans-effect. Two additive components are revealed within the trans-effect, namely the inter-bond charge transfer and the induced dipole moment of the Cβ–Cγ (or Cβ–H) bond under the influence of the Z–Cα bond. These components and thereby the whole effect are expressed and interpreted in terms of through-space and through-bond interactions of bond orbitals. Comparison of the trans-effect of heteroatom to the inductive effect also is carried out.
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