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Nucleophilic Substitution in Solution: Activation Strain Analysis of Weak and Strong Solvent Effects
Author(s) -
Hamlin Trevor A.,
van Beek Bas,
Wolters Lando P.,
Bickelhaupt F. Matthias
Publication year - 2018
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.201706075
Subject(s) - chemistry , solvation , nucleophile , reaction coordinate , solvent effects , solvent , nucleophilic substitution , computational chemistry , transition state , leaving group , substitution reaction , density functional theory , photochemistry , chemical physics , organic chemistry , catalysis
We have quantum chemically studied the effect of various polar and apolar solvents on the shape of the potential energy surface (PES) of a diverse collection of archetypal nucleophilic substitution reactions at carbon, silicon, phosphorus, and arsenic by using density functional theory at the OLYP/TZ2P level. In the gas phase, all our model S N 2 reactions have single‐well PESs, except for the nucleophilic substitution reaction at carbon (S N 2@C), which has a double‐well energy profile. The presence of the solvent can have a significant effect on the shape of the PES and, thus, on the nature of the S N 2 process. Solvation energies, charges on the nucleophile or leaving group, and structural features are compared for the various S N 2 reactions in a spectrum of solvents. We demonstrate how solvation can change the shape of the PES, depending not only on the polarity of the solvent, but also on how the charge is distributed over the interacting molecular moieties during different stages of the reaction. In the case of a nucleophilic substitution at three‐coordinate phosphorus, the reaction can be made to proceed through a single‐well [no transition state (TS)], bimodal barrier (two TSs), and then through a unimodal transition state (one TS) simply by increasing the polarity of the solvent.