Negative hyperconjugation in acidity of polyfluorinated alkanes. A natural bond orbital analysis

Masahiko Suenaga, Kazuhide Nakata, José Luis M. Abboud, Masaaki Mishima

Research output: Contribution to journalArticle

Abstract

Natural bond orbital (NBO) analysis has been applied to various polyfluorinated carbanions. The E(2)[LP(Cα)→σ∗(Cβ-F) or σ∗(Cβ-Cγ)] values that are interaction energies between a lone pair NBO at the anionic center carbon and the σ∗(Cβ-F) or σ∗(Cβ-Cγ) NBO increased with the corresponding Cβ-F or Cβ-Cγ bond distances, respectively, being consistent with the molecular orbital theory on negative hyperconjugation. The total E(2) values for the interactions of a lone pair orbital with all σ∗(Cβ-F) and σ∗(Cβ-Cγ) orbitals were linearly correlated with gas-phase acidities of the corresponding alkanes, giving two lines for the carbanions having no β-fluorine atom and for the primary and secondary carbanions having β-fluorine atoms (slopes of 0.57 and 1.56, respectively). The major E(2)[LP(Cα)→σ∗(Cβ-F)] values in the respective anions were found to be linearly correlated with the ΔG°β-F values as an empirical measure of β-fluorine negative hyperconjugation obtained from an increased acidity of the molecule owing to the presence of β-fluorine. However, the magnitude of ΔG°β-F was much smaller than the E(2)[LP(Cα)→σ∗(Cβ-F)] value, indicating that the absolute values of the β-fluorine negative hyperconjugation are smaller than the E(2) interaction energies.

Original languageEnglish
Pages (from-to)289-297
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume90
Issue number3
DOIs
Publication statusPublished - Jan 1 2017

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Alkanes
Fluorine
Acidity
Atoms
Molecular orbitals
Anions
Carbon
Gases
Molecules

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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Negative hyperconjugation in acidity of polyfluorinated alkanes. A natural bond orbital analysis. / Suenaga, Masahiko; Nakata, Kazuhide; Abboud, José Luis M.; Mishima, Masaaki.

In: Bulletin of the Chemical Society of Japan, Vol. 90, No. 3, 01.01.2017, p. 289-297.

Research output: Contribution to journalArticle

Suenaga, Masahiko ; Nakata, Kazuhide ; Abboud, José Luis M. ; Mishima, Masaaki. / Negative hyperconjugation in acidity of polyfluorinated alkanes. A natural bond orbital analysis. In: Bulletin of the Chemical Society of Japan. 2017 ; Vol. 90, No. 3. pp. 289-297.
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