Spectroscopic Study of the Br- +CH3 I→I- +CH3 Br SN 2 Reaction

Chemphyschem. 2022 Nov 4;23(21):e202200278. doi: 10.1002/cphc.202200278. Epub 2022 Aug 11.

Abstract

Mass spectrometry and anion photoelectron spectroscopy have been used to study the gas-phase S N 2 ${{{\rm S}}_{{\rm N}}2}$ reaction involving B r - ${{{\rm B}{\rm r}}^{-}}$ and C H 3 I ${{{\rm C}{\rm H}}_{3}{\rm I}}$ . The anion photoelectron spectra associated with the reaction intermediates of this S N 2 ${{{\rm S}}_{{\rm N}}2}$ reaction are presented. High-level CCSD(T) calculations have been utilised to investigate the reaction intermediates that may form as a result of the S N 2 ${{{\rm S}}_{{\rm N}}2}$ reaction along various different reaction pathways, including back-side attack and front-side attack. In addition, simulated vertical detachment energies of each reaction intermediate have been calculated to rationalise the photoelectron spectra.

Keywords: ab initio calculations; halides; noncovalent interactions; nucleophilic substitution; photoelectron spectroscopy.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry
  • Photoelectron Spectroscopy
  • Quantum Theory*

Substances

  • Anions