Nucleophilic Substitution in Solution: Activation Strain Analysis of Weak and Strong Solvent Effects.

ABSTRACT: 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

SUBMITTER: Hamlin TA 

PROVIDER: S-EPMC5947303 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature