| Autor: |
East AL; Department of Chemistry and Biochemistry, University of Regina, Regina, Saskatchewan, S4S 0A2, Canada., Grittner KL, Afzal AI, Simpson AG, Liebman JF |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2005 Dec 22; Vol. 109 (50), pp. 11424-8. |
| DOI: |
10.1021/jp053391i |
| Abstrakt: |
Conjugated polyynes are a class of species of diverse and increasing interest. Length-scrambling and substituent scrambling reaction energies were examined using ab initio quantum chemistry calculations to investigate issues concerning the energetic effects of the molecular ends (substituent communication). Computations were performed for the parent, monohalogenated, and dihalogenated (F, Cl, Br, I) polyynes of up to 60 carbon atoms. A study of resonance effects using natural resonance theory and bond lengths demonstrates lone-pair-donating effects that increase in the series F < Cl < Br < I, but run counter to the halogen inductive effects which decrease in this series and dominate energetic effects. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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