Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH3S-S(H)CH3 and (CH3SH)2+ and Enhancement of the 3e-2c Bond upon Protonation

Min Xie, Zhitao Shen, Dandan Wang, Asuka Fujii, Yuan Pern Lee

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6 Citations (Scopus)

Abstract

The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH3S-S(H)CH3 and the strongly 3e-2c-bound (CH3SH)2+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH3S-S(H)CH3 to form [CH3(H)S-S(H)CH3]+ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol-1.

Original languageEnglish
Pages (from-to)3725-3730
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume9
Issue number13
DOIs
Publication statusPublished - 2018 Jul 5

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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