Indices for predicting the quality of leaving groups

Paul W. Ayers, James S.M. Anderson, Juan I. Rodriguez, Zobia Jawed

Research output: Contribution to journalArticle

104 Citations (Scopus)

Abstract

The inherent quality of leaving groups in chemical reactions is related to their ionization potential and electron affinity using a quadratic model for the dependence of the energy on the number of electrons. A good leaving group for nucleophilic substitution/elimination reactions is one where the difference in energy between the system with the "optimum" number of electrons and the anion is small. Similarly, a good leaving group for electrophilic substitution/elimination reactions is one where the difference in energy between the system with the optimum number of electrons and the cation is small. This insight allows us to define indices for the quality of leaving groups in nucleophilic and electrophilic reactivity, which we term the nucleofugality and the electrofugality, respectively. These indices are useful not only for predicting the quality of leaving groups in organic reactions, but also for explaining the stability of carbocations, carbanions, and trends in pK a. © The Owner Societies 2005.
Original languageAmerican English
Pages (from-to)1918-1925
Number of pages1725
JournalPhysical Chemistry Chemical Physics
DOIs
StatePublished - 7 May 2005
Externally publishedYes

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Electrons
Substitution reactions
Electron affinity
Ionization potential
elimination
Anions
Cations
Chemical reactions
substitutes
electrons
electron affinity
ionization potentials
affinity
energy
chemical reactions
reactivity
anions
trends
cations

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Ayers, Paul W. ; Anderson, James S.M. ; Rodriguez, Juan I. ; Jawed, Zobia. / Indices for predicting the quality of leaving groups. In: Physical Chemistry Chemical Physics. 2005 ; pp. 1918-1925.
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Indices for predicting the quality of leaving groups. / Ayers, Paul W.; Anderson, James S.M.; Rodriguez, Juan I.; Jawed, Zobia.

In: Physical Chemistry Chemical Physics, 07.05.2005, p. 1918-1925.

Research output: Contribution to journalArticle

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