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

doi:10.1016/j.molstruc.2017.09.063

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 journal › Article › peer-review

3 Citations (Scopus)

Abstract

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 language	English
Pages (from-to)	215-222
Number of pages	8
Journal	Journal of Molecular Structure
Volume	1152
DOIs	https://doi.org/10.1016/j.molstruc.2017.09.063
Publication status	Published - 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.

Keywords

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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10.1016/j.molstruc.2017.09.063

Cite this

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title = "Hindered C–N bond rotation in triazinyl dithiocarbamates",

abstract = "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.",

keywords = "C–N bond rotational dynamics, DFT calculation, Dithiocarbamate, Triazinyl derivative, VT-NMR",

author = "Taesub Jung and Do, {Hee Jin} and Jongwoo Son and Song, {Jae Hee} and Wansik Cha and Kim, {Yeong Joon} and Lee, {Kyung Koo} and Kyungwon Kwak",

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: {\textcopyright} 2017 Elsevier B.V.",

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doi = "10.1016/j.molstruc.2017.09.063",

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T1 - Hindered C–N bond rotation in triazinyl dithiocarbamates

AU - Jung, Taesub

AU - Do, Hee Jin

AU - Son, Jongwoo

AU - Song, Jae Hee

AU - Cha, Wansik

AU - Kim, Yeong Joon

AU - Lee, Kyung Koo

AU - Kwak, Kyungwon

N1 - 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.

PY - 2018/1/15

Y1 - 2018/1/15

N2 - 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.

AB - 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.

KW - C–N bond rotational dynamics

KW - DFT calculation

KW - Dithiocarbamate

KW - Triazinyl derivative

KW - VT-NMR

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JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

Hindered C–N bond rotation in triazinyl dithiocarbamates

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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