Tautomerism in 4-chlorophenyl benzoylcarbamodithioate: Experimental and DFT study
[ X ]
Tarih
2017
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Elsevier Science Bv
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
The title dithiocarbamate compound was synthesized, and characterised by means of spectroscopic and single-crystal X-ray diffraction methods. Density functional theory method with the 6-311++G(d,p) basis set was employed to affirm the spectroscopic and structural properties and also to study the tautomerism in the compound. The obtained theoretical parameters clearly support the experimental findings. Among the six structural forms of the title compound, the syn-keto-amine-thione is found to be the most stable one, and the stability sequence is as the followings: syn-keto-amine-thione > anti-enolimine-thione > anti-keto-amine-thione > anti-keto-imine-thiol > syn-keto-imine-thiol > syn-enolimine-thione. The energy difference between the anti and syn forms changes from ca. 8-59 kJ morl(-1) with or without barriers. The energetic and thermodynamic findings of the syn-lceto-amine-thione reversible arrow syn-keto-irnine-thiol reaction display that the single proton exchange is unfavoured in both directions. Although the reverse barrier energy of the anti-enol-imine-thione reversible arrow anti-keto-imine-thiol tautomeric transformation is found to be small, neither the forward nor the reverse reaction appears to happen from the thermodynamic point of view. (C) 2017 Elsevier B.V. All rights reserved.
Açıklama
Anahtar Kelimeler
Crystal structure, Spectroscopy, Density functional theory, Rotamerism, Tautomerism
Kaynak
Journal of Molecular Structure
WoS Q Değeri
Q3
Scopus Q Değeri
Q1
Cilt
1137
