Hindered C–N bond rotation in triazinyl dithiocarbamates

Taesub Jung, Hee Jin Do, Jongwoo Son, Jae Hee Song, Wansik Cha, Yeong Joon Kim, Kyung Koo Lee, Kyungwon Kwak

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)


The substituent and solvent effects on the rotation around a C–N amide bond were studied for a series of triazine dibenzylcarbamodithioates. The Gibbs free energies (ΔG) were measured to be 16–18 kcal/mol in DMSO-d6 and toluene-d8 using variable-temperature nuclear magnetic resonance (VT-1H NMR) spectroscopy. Density functional theory (DFT) calculations reproduced the experimental observations with various substituents, as well as solvents. From the detailed analysis of the DFT results, we found that the electron donating dibenzyl amine group increased the electron population on the triazinyl ring, which decreased the rotational barrier of the C–N bond in the dithiocarbamate group attached to the triazinyl ring. The higher electron population on the triazine moiety stabilizes the partial double bond character of the S–C bond, which competitively excludes the double bond character of the C–N bond. Therefore, the rotational dynamics of the C–N bond in dithiocarbamates can be a sensitive probe to small differences in the electron population of substituents on sulfur.

Original languageEnglish
Pages (from-to)215-222
Number of pages8
JournalJournal of Molecular Structure
Publication statusPublished - 2018 Jan 15

Bibliographical note

Funding Information:
This research was supported by the Nuclear Research and Development Program of the National Research Foundation of Korea [Grant No. NRF-2016M2A8A5021714 ]. Y.-J. Kim acknowledges support from the Research Fund at Chungnam National University . We thank Mr. Shinho Lee for help with preliminary experiments.

Publisher Copyright:
© 2017 Elsevier B.V.


  • C–N bond rotational dynamics
  • DFT calculation
  • Dithiocarbamate
  • Triazinyl derivative
  • VT-NMR

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry


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