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The Rates of S N 2 Reactions and Their Relation to Molecular and Solvent Properties
Author(s) -
Arnaut Luis G.,
Formosinho Sebastião J.
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700276
Subject(s) - nucleophile , chemistry , electrophile , solvent , reactivity (psychology) , computational chemistry , reaction rate constant , solvent effects , molecule , electron transfer , thermodynamics , kinetics , organic chemistry , physics , quantum mechanics , catalysis , medicine , alternative medicine , pathology
The energy barriers of symmetrical methyl exchanges in the gas phase have been calculated with the reaction path of the intersecting/interacting‐state model (ISM). Reactive bond lengths increase down a column of the Periodic Table and compensate for the decrease in the force constants, which explains the near constancy of the intrinsic barriers in the following series of nucleophiles: F − ≈Cl − ≈Br − ≈I − . This compensation is absent along the rows of the Periodic Table and the trend in the reactivity is dominated by the increase in the electrophilicity index of the nucleophile in the series C