Spectroscopy, structure, thermal and photochemical decomposition of 5-chloro-3-trifluoromethyl-1,2,4-thiadiazole: Generation of trifluoroacetonitrile N-sulfide

T. Pasinszki, Tamás Vörös, Gábor Vass, G. Tarczay, István Jalsovszky

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Abstract

The structure and thermal and photochemical decomposition of the synthetic precursor 5-chloro-3-trifluoromethyl-1,2,4-thiadiazole (1) have been investigated for the first time by mid-infrared, Raman, ultraviolet and He I photoelectron spectroscopy. Spectroscopies, supported by quantum-chemical calculations using the B3LYP and SAC-CI methods, provided a detailed investigation into the vibrational and electronic character of the molecule. Thermal stability and photochemical decomposition of 1 have been studied in the gas phase and solid matrix, respectively. Flash vacuum thermolysis of the molecule produced fast quantitatively CF3CN, ClCN, and sulfur. However, UV irradiation of 1 in solid argon matrix at selected wavelengths of 213, 228, 240, and 250 nm resulted in a retro-cycloaddition reaction leading to the formation of a novel nitrile sulfide, CF3CNS (2), and ClCN. The structure of 2 was computed at the B3LYP and CCSD(T)/aug-cc-pVTZ levels, and its IR identification was supported by quantum chemical calculations.

Original languageEnglish
Pages (from-to)118-125
Number of pages8
JournalJournal of Molecular Structure
Volume1179
DOIs
Publication statusPublished - Mar 5 2019

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Keywords

  • 1,2,4-Tiadiazole
  • Nitrile sulfide
  • Photolysis
  • Spectroscopy
  • Structure
  • Thermolysis

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

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