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Anomalous Selectivities in Methyl Transfers to Water: An Explanation Using Free Energy Surfaces which Model the Effects of Non‐Equilibrium Solvation
Author(s) -
Kurz Joseph L.,
Kurz Linda C.
Publication year - 1985
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198500117
Subject(s) - chemistry , solvation , solvent , polarization (electrochemistry) , transition state , solvent effects , chemical physics , solvation shell , computational chemistry , water model , thermodynamics , molecular dynamics , organic chemistry , catalysis , physics
Many experimental observations imply that transition states for methyl‐transfers to water have little or no water—methyl covalent bonding and that the rate‐determining process is predominantly or entirely a fluctuation in solvent structure. Currently accepted descriptions of methyl‐transfer mechanisms cannot easily account for such a transition state structure or for the anomalous selectivities observed in these reactions. This paper derives a model free energy surface, which includes solvent polarization as one of the coordinates, and shows how that surface can account for the observed behavior of these methyl‐transfers. The transition state on that surface has a structure in which the solvent polarization is not in equilibrium with the internal charge distribution.