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https://doi.org/10.5562/cca1794

The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles

Viktorija Gineityte ; Institute of Theoretical Physics and Astronomy, Vilnius University, Gostauto 12, LT-01108 Vilnius, Lithuania

Puni tekst: engleski, pdf (1 MB) str. 171-185 preuzimanja: 490* citiraj
APA 6th Edition
Gineityte, V. (2013). The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles. Croatica Chemica Acta, 86 (2), 171-185. https://doi.org/10.5562/cca1794
MLA 8th Edition
Gineityte, Viktorija. "The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles." Croatica Chemica Acta, vol. 86, br. 2, 2013, str. 171-185. https://doi.org/10.5562/cca1794. Citirano 18.09.2020.
Chicago 17th Edition
Gineityte, Viktorija. "The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles." Croatica Chemica Acta 86, br. 2 (2013): 171-185. https://doi.org/10.5562/cca1794
Harvard
Gineityte, V. (2013). 'The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles', Croatica Chemica Acta, 86(2), str. 171-185. https://doi.org/10.5562/cca1794
Vancouver
Gineityte V. The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles. Croatica Chemica Acta [Internet]. 2013 [pristupljeno 18.09.2020.];86(2):171-185. https://doi.org/10.5562/cca1794
IEEE
V. Gineityte, "The Rule of Suppressed Charge Transfer between Heteroaromatic Compounds and Electrophiles", Croatica Chemica Acta, vol.86, br. 2, str. 171-185, 2013. [Online]. https://doi.org/10.5562/cca1794

Sažetak
Replacement of a carbon atom of an aromatic compound by a more electronegative heteroatom
gives rise to suppression of reactivities of the remaining carbon atoms in electrophilic substitution (SE2)
reactions. To prove this experiment-based rule, the reactivities are related to the relevant extents of the
intermolecular charge transfer. General algebraic expressions are derived and analyzed for these extents
for various directions of the attack of electrophile. The reactant is considered as a perturbed alternant
hydrocarbon, the perturbation coinciding with the alteration in the Coulomb parameter of the carbon atom
undergoing the replacement, whereas the reagent is represented explicitly by an external vacant orbital.
Changes in the intermolecular charge transfer due to introduction of heteroatom are shown to consist of
two components, viz. of an initial-population-dependent component contributing increments of alternating
signs for shifting positions of electrophile along the hydrocarbon chain and of an additional negative
contribution originating from the increased interval between diagonal Hamiltonian matrix elements for
orbitals participating in the charge transfer. For soft electrophiles, the negative contribution is shown to
predominate over the alternating one. This implies the charge transfer between heteroaromatic reactants
and electrophiles to be suppressed vs. the relevant values for hydrocarbons-containing system. (doi:
10.5562/cca1794)

Ključne riječi
alternant conjugated hydrocarbons; the Hückel model; chemical reactivity; electrophilic aromatic substitution; soft electrophiles

Hrčak ID: 105583

URI
https://hrcak.srce.hr/105583

Posjeta: 721 *