Hindered C–N bond rotation in triazinyl dithiocarbamates

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Title
Hindered C–N bond rotation in triazinyl dithiocarbamates
Author(s)
Taesub Jung; Hee-Jin Do; Jongwoo Son; Jae Hee Song; Wansik Cha; Yeong-Joon Kim; Kyung-Koo Lee; Kyungwon Kwak
Publication Date
2018-01
Journal
JOURNAL OF MOLECULAR STRUCTURE, v.1152, no., pp.215 - 222
Publisher
ELSEVIER SCIENCE BV
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. © 2017 Elsevier B.V
URI
https://pr.ibs.re.kr/handle/8788114/3976
ISSN
0022-2860
Appears in Collections:
Center for Molecular Spectroscopy and Dynamics(분자 분광학 및 동력학 연구단) > Journal Papers (저널논문)
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