Molecular structure and thermal stability of α-halogen-<Emphasis Type="Italic">gem</Emphasis>-dithiols |
| |
Authors: | V A Shagun L G Shagun L P Ermolyuk M G Voronkov |
| |
Institution: | (1) A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033 Irkutsk, Russian Federation |
| |
Abstract: | The electronic structure of α-halogen-gem-dithiols RC(SH)2CH2X (R = Me, Ph; X = F, Cl, Br, I) was studied by quantum chemistry methods. Four most stable rotamers were located, differing in the mutual orientation of the thiol groups and the halogen atom. The thermodynamic and kinetic characteristics of the thermolysis of α-halogen-gem-dithiols were obtained. Thermolysis of chlorine- and bromine-substituted gem-dithiols depends on the properties of the medium, namely, in aprotic media aromatic dithiols form trithianorbornane derivatives while aliphatic dithiols form thiirane derivatives. In an aqueous medium (R = Me, Ph), water promoted elimination of hydrogen sulfide with the formation of corresponding thiones is more preferable. Thermolysis of aliphatic iodine-substituted gem-dithiols proceeds as bimolecular deiodination resulting in the formation of a new C-C bond.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 559–568, March, 2005. |
| |
Keywords: | quantum-chemical calculations α -halogen-gem-dithiols rotational isomerism thermolysis potential energy surface mechanism |
本文献已被 SpringerLink 等数据库收录! |
|